Hydroxylamine ethers

ABSTRACT

There are disclosed a pyrazole compound represented by the formula ##STR1## wherein the substituents of R 1  to R 7  and the symbol Z have the specified meanings as described in the text, an insecticidal, acaricidal and fungicidal composition containing the same, use of said composition for control of insects, acarids and fungi and a method of preparing said compound, and its intermediate.

This is a division of application Ser. No. 07/410,425, filed Sept. 21,1989, now U.S. Pat. No. 4,980,345

The present invention relates to a novel pyrazole compound, a method forits production, an insecticidal, acaricidal and fungicidal compositioncontaining it as an active ingredient and intermediates for producingit.

It is disclosed in EP 234,045-A2 and JP-A-64-13086 that certain pyrazolecompounds have insecticidal, acaricidal and fungicidal activity.

These compounds, however, may not always be said to be satisfactory interms of the efficiency efficacy and spectrum of their activities.

In view of such situation, the present inventors have extensivelystudied to develop a compound having excellent activity, and as aresult, have found that the pyrazole compound represented by thefollowing formula (I) has particularly excellent insecticidal,acaricidal, and fungicidal activity. The present inventors thus havecompleted the present invention.

The present invention provides a pyrazole compound represented by theformula (I) [hereinafter referred to as present compound(s)], a methodfor its production, an insecticidal, acaricidal, and fungicidalcomposition containing it as an active ingredient and intermediates forproducing it: ##STR2## wherein R₁ is a hydrogen atom, or an alkyl orphenyl group; R₂ is a hydrogen atom, or an alkyl or haloalkyl group; R₃is a hydrogen atom, or an alkyl or phenyl group; each of R₄ and R₅,which may be the same or different, is a hydrogen atom or an alkylgroup; R₆ is a hydrogen atom, or an alkyl, haloalkyl, alkenyl,alkoxyalkyl, alkylthioalkyl, trialkylsilyl or dialkylphenyl silyl group,or an optionally substituted cycloalkyl, cycloalkenyl, phenyl or pyridylgroup; R₇ is an alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl,haloalkynyl, alkoxyalkyl, alkylthioalkyl or mono or dialkylaminoalkylgroup, or an optionally substituted cycloalkyl or cycloalkenyl group, ora group represented by ##STR3## (in which X is an oxygen or sulfuratom), or a group represented by ##STR4## (in which each of V's, whichmay be the same or different, is a hydrogen or halogen atom, or analkyl, haloalkyl, alkoxyl, haloalkoxyl or methylenedioxy group, A is anitrogen atom or a methine group, and n is an integer of from 1 to 5);and Z is an oxygen or sulfur atom.

Where the present compound represented by the formula (I) contains oneor more asymmetric carbon atoms, the compound may be an optical isomerin (+)-form, (-)-form or mixture thereof, and further, where thecompound includes geometric isomers in its structure, it may be acis-form, trans-form or mixture thereof.

The formula (I) representing the present compounds will be explainedbelow.

In the definitions of R₁, the alkyl group is preferably a C₁ -C₄ alkylgroup. In the definitions of R₂, the alkyl and haloalkyl groups arepreferably a C₁ -C₄ alkyl group and may be substituted with chlorine,bromine or fluorine, respectively. In the definitions of R₃, the alkylgroup is preferably a C₁ -C₂ alkyl group. In the definitions of R₄ andR₅, the alkyl group is preferably a C₁ -C₃ alkyl group. In thedefinitions of R₆, the alkyl, haloalkyl, alkenyl, alkoxyalkyl,alkylthioalkyl, cycloalkyl, and cycloalkenyl groups are preferably a C₁-C₈ alkyl group, a C₁ -C₈ alkyl group substituted with a chlorine,bromine or fluorine atom, a C₂ -C₈ alkenyl group, a C₂ -C₈ alkoxyalkylgroup, a C₂ -C₈ alkylthioalkyl group, a C₃ -C₈ cycloalkyl group and a C₃-C₈ cycloalkenyl group, respectively, and the substituents substitutedon the cycloalkyl, cycloalkenyl, phenyl and pyridyl groups include a C₁-C₃ alkyl group, a C₁ -C₃ alkoxy group and a halogen atom (e.g.chlorine, bromine, fluorine). The alkyl moieties of the trialkylsilyl ordialkylphenylsilyl group include a C₁ -C₂ alkyl group. In thedefinitions of R₇, the alkyl, alkenyl and alkynyl groups are preferablythose having 1(2) to 8 carbon atoms; the haloalkyl, haloalkenyl andhaloalkynyl groups are preferably those having 1(2) to 8 carbon atomssubstituted with a chlorine, bromine or fluorine atom; the alkoxyalkyl,alkylthioalkyl and mono or dialkylaminoalkyl groups are preferably thosehaving 2 to 10 carbon atoms; the cycloalkyl and cycloalkenyl groups arepreferably a C₃ -C₈ cycloalkyl and cycloalkenyl groups, respectively;and the substituents subsituted on the cycloalkyl and cycloalkenylgroups include a C₁ -C₃ alkyl group, a C₁ -C₃ alkoxy group and a halogenatom (e.g. chlorine, bromine, fluorine). In the definitions of V, thehalogen atom is preferably a chlorine, bromine or fluorine atom; thealkyl group is preferably a C₁ -C₄ alkyl group; the haloalkyl group ispreferably a C₁ -C₂ alkyl group substituted with a chlorine, bromine orfluorine atom; the alkoxyl group is preferably a C₁ -C₄ alkoxyl group;and the haloalkoxyl group is preferably a C₁ -C₄ alkoxyl groupsubstituted with a chlorine, bromine or fluorine atom.

Preferred compounds of the present invention, include those representedby the formula (I) in which R₁ is a hydrogen atom or an alkyl group, R₂is a methyl group, and R₃ is a hydrogen atom. More preferred ones,include those represented by the formula (I) in which all of R₄, R₅ andR₆ are hydrogen atoms and R₁, R₂ and R₃ have the same meanings asmentioned above. As illustrative examples, the following compounds maybe nominated:

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-fluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(3,5-difluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-5-trimethylsilylpent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-5-(dimethylphenylsilyl)pent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyloct-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6-methylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-5-cyclohexylpent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoropent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-5-phenylpent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-isopropyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-methylphenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-methoxyphenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-fluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(m-fluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(3,5-difluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-methylphenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(p-methoxyphenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(m-fluorophenoxy)pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-sec-butyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether;

1,3-Dimethyl-5-sec-butyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-(2,2,3,3,3-pentafluoro-n-propyloxy)-pyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhex-2-ene-4-ynyl ether;

1,3-Dimethyl-5-sec-butyloxypyrazol-4-carboaldoximeO-2-fluoro-5trimethylsilylpent-2-ene-4-ynyl ether;

1,3-Dimethyl-5-sec-butyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyloct-2-ene-4-ynyl ether;

1,3-Dimethyl-5-cyclohexyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

Insect pests against which the present compounds are effective includeHemiptera such as planthoppers, leafhoppers, aphids, bugs, whiteflies,etc.; Lepidoptera such as diamond-back moth (Plutella xylostella), ricestem boxer (Chilo suppressalis), rice leafroller (Cnaphalocrocismedinalis), armyworms and cutworms, Plusiid moths (Plusiinae), smallwhite butterfly (Pieris rapae crucivora), casemaking clothes moth (Tineapellionella), webbing clothes moth (Tineola bisselliella), etc.; Dipterasuch as common mosquito (Culex pipiens pallens), Anopheline mosquito(Anopheles spp.), Aedes mosquito (Aedes spp.), housefly (Muscadomestica), etc.; Dictyoptera such as German cockroach (Blattellagermanica), smokybrown cockroach (Periplaneta fuliginosa), browncockroach (Periplaneta brunnea), American cockroach (Periplanetaamericana), etc.; Coleoptera, Hymenoptera, Thysanoptera, Orthoptera,etc.; and spider mites such as carmine spider mite (Tetranychuscinnabarinus), two-spotted spider mite (Tetranychus urticae), citrus redmite (Panonychus citri), etc. Further, the present compounds are alsoeffective against insect pests having an increased resistance to theexisting insecticides and acaricides.

Further, the present compounds exhibit excellent controlling effects interms of a preventive effect, a curative effect or a systemic effect onvarious plant diseases.

As plant diseases on which the present compounds have excellentcontrolling effect, examples are: blast of rice (Pyricularia oryzae),helminthosporium leaf spot of rice (Cochliobolus miyabeanus), sheathblight of rice (Rhizoctonia solani), powdery mildew of wheat and barley(Erysiphe graminis f. sp. hordei and E. g. f. sp. tritici), net blotchof wheat and barley (Pyrenophora teres), fusarium blight of wheat andbarley (Gibberella zeae), rust of wheat and barley (Pucciniastriiformis, P. graminis, P. recondita and P. hordei), snow blight ofwheat and barley (Typhula sp. and Micronectriella nivalis), loose smutof wheat and barley (Ustilago tritici and U. nuda), bunt of wheat andbarley (Tilletia caries), eye spot of wheat and barley(Pseudocercosporella herpotrichoides), leaf blotch of wheat and barley(Rhynchosporium secalis), speckled leaf blotch of wheat and barley(Septoria tritici), glume blotch of wheat and barley (Leptosphaerianodorum), melanose of citrus (Diaporthe citri), scab of citrus (Elsinoefawcetti), fruit rot of citrus (Penicillium digitatum and P. italicum ),blossom blight of apple (Sclerotinia mali), canker of apple (Valsamali), powdery mildew of apple (Podosphaera leucotricha), alternarialeaf spot of apple (Alternaria mali), scab of apple (Venturiainaequalis), scab of pear (Venturia nashicola and V. pirina), black spotof pear (Alternaria kikuchiana), rust of pear (Gymnosporangiumharaeanum), brown rot of peach (Sclerotinia cinerea), scab of peach(Cladosporium carpophilum), phomopsis rot of peach (Phomopsis sp.),anthracnose of grape (Elsinoe ampelina), ripe rot of grape (Glomerellacingulata), powdery mildew of grape (Uncinula necator), rust of grape(Phakopsora ampelopsidis), black rot of grape (Guignardia bidwellii),downy mildew of grape (Plasmopara viticola), anthracnose of Japanesepersimmon (Gloeosporium kaki), leaf spot of Japanese persimmon(Cercospora kaki and Mycosphaerella nawae), anthracnose of cucumber(Colletotrichum lagenarium), powdery mildew of cucumber (Sphaerothecafuliginea), gummy stem blight of cucumber (Mycosphaerella melonis),downy mildew of cucumber (Pseudoperonospora cubensis), early blight oftomato (Alternaria solani), leaf mold of tomato (Cladosporium fulvum),late blight of tomato (Phytophthora infestans), phomopsis blight ofeggplant (Phomopsis vexans ), powdery mildew of eggplant (Erysiphecichoracearum), alternaria leaf spot of brassica (Alternaria japonica),white spot of brassica (Cercosporella brassicae), rust of Welsh onion(Puccinia allii), purple stain of soybean (Cercospora kikuchii),anthracnose of soybean (Elsinoe glycines), melanose of soybean(Diaporthe phaseolorum var. sojae), anthracnose of kidney bean(Colletotrichum lindemuthianum), leaf spot of peanut (Mycosphaerellapersonatum), brown leaf spot of peanut (Cercospora arachidicola),powdery mildew of pea (Erysiphe pisi), early blight of potato(Alternaria solani), late blight of potato (Phytophthora infestans),powdery mildew of strawberry (Sphaerotheca humuli), net blister blightof tea (Exobasidium reticulatum), white scab of tea (Elsinoeleucospila), brown spot of tobacco (Alternaria longipes), powdery mildewof tobacco (Erysiphe cichoracearum), anthracnose of tobacco(Colletorichum tabacum), cercospora leaf spot of beet (Cercosporabeticola), scab of rose (Diplocarpon rosae), powdery mildew of rose(Sphaerotheca pannosa), leaf blight of chrysanthemum (Septoriachrysanthemiindici), rust of chrysanthemum (Puccinia horiana), gray mold(Botrytis cinerea) and stem rot (Sclerotinia sclerotiorum) of variouscrops, and the like.

Of the present compounds, those represented by the following formula(I') can be produced, for example, by the following method A, B or C:##STR5## wherein R₁, R₂, R₃, R₄, R₅, R₇ and Z are as defined above; andR'₆ is a hydrogen atom, or an alkyl, haloalkyl, alkenyl, alkoxyalkyl oralkylthioalkyl group, or an optionally substituted cycloalkyl,cycloalkenyl, phenyl or pyridyl group.

METHOD A

A method for producing the present compounds (I') compromising reactinga compound represented by the formula (II), ##STR6## wherein R₁, R₂, R₃,R₇ and Z are as defined above, with a compound represented by theformula (III), ##STR7## wherein R₄, R₅ and R'₆ are as defined above; andW₁ is a halogen atom.

METHOD B

A second method for producing the present compounds (I') compromisesreacting a compound represented by the formula (IV), ##STR8## whereinR₁, R₂, R₃, R₇ and Z are as defined above, with a compound representedby the formula (V), ##STR9## wherein R₄, R₅ and R'₆ are as definedabove.

METHOD C

A third method for producing the present compounds (I') compromisesreacting a compound represented by the formula (II), ##STR10## whereinR₁, R₂, R₃, R₇ and Z are as defined above, with a compound representedby the formula (VI), ##STR11## wherein R₄, R₅ and R'₆ are as definedabove; and W₂ is a halogen atom.

In Methods A and C, a solvent is not always necessary for the reaction,but when a solvent is used, the following solvents are examples of thoseused: Ethers (e.g. diethyl ether, tetrahydrofuran, dioxane), alcohols(e.g. ethylene glycol, glycerin, methanol, ethanol), acid amides (e.g.N,N-dimethylformamide, N,N-dimethylacetamide), sulfolane, dimethylsulfoxide, aromatic hydrocarbons (e.g. benzene, toluene, chlorobenzene),halogenated hydrocarbons (e.g. methylene chloride, chloroform), ketones(e.g. acetone, methyl isobutyl ketone), nitriles (e.g. acetonitrile,benzonitrile), pyridines (e.g. pyridine, picoline), water and mixturesof these solvents. The compound of the formula (III) or (VI) is used inan amount of from 0.5 to 10 moles per 1 mole of the compound of theformula (II). The reaction temperature is usually from -20° to 200° C.,preferably, from -10° to 100° C. The reaction time is usually from 5minutes to 100 hours, preferably, from 30 minutes to 50 hours.

Usually, in carrying out this reaction, the following compounds are usedas an acid-binding agent: Alkali metal hydroxides (e.g. lithiumhydroxide, sodium hydroxide, potassium hydroxide), alkali metalcarbonates (e.g. sodium carbonate, potassium carbonate), alkali metalhydrides (e.g. lithium hydride, sodium hydride, potassium hydride),alkali metals (e.g. metallic lithium, metallic sodium, metallicpotassium), alkali metal alkoxides (e.g. sodium methoxide, sodiumethoxide) and mixtures thereof. The amount of the acid-binding agentused is from 0.5 to 10 moles for 1 mole of the compound of the formula(II). If necessary, a phase transfer catalyst such as ammonium salts(e.g. tetra-n-butylammonium bromide, benzyltrimethylammonium chloride),ethers (e.g. 18-Crown-6), amines [e.g. tris(3,6-dioxoheptyl)amine(TDA-1)], etc. may also be used in an amount of from 0.0001 to 1 moleper 1 mole of the compound of the formula (II).

After completion of the reaction, the desired present compounds can beobtained by the conventional after-treatments.

In Method B, a solvent is not always necessary for the reaction, butwhen a solvent is used, the following solvents can be used: Ethers (e.g.diethyl ether, tetrahydrofuran, dioxane), alcohols (e.g. ethyleneglycol, glycerin, methanol, ethanol), acid amides (e.g.N,N-dimethylformamide, N,N-dimethylacetamide), sulfolane, dimethylsulfoxide, aromatic hydrocarbons (e.g. benzene, toleuene,chlorobenzene), halogenated hydrocarbons (e.g. methylene chloride,chloroform), aliphatic hydrocarbons (e.g. pentane, hexane, heptane,cyclohexane), pyridines (e.g. pyridine, picoline), acetic acid, waterand mixtures of these solvents. The compound of the formula (V) is usedin an amount of from 0.5 to 10 moles per 1 mole of the compound of theformula (IV). The reaction temperature is usually from -20° to 200° C.,preferably, from -10° to 150° C. The reaction time is usually from 5minutes to 100 hours, preferably, from 5 minutes to 20 hours. Ifnecessary, the following agents may be used as a catalyst for reaction:Mineral acids (e.g. hydrochloric acid, sulfuric acid, nitric acid),organic acids (e.g. formic acid, acetic acid, propionic acid,methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid),amine/acid adducts (e.g. pyridine hydrochloride, triethylaminehydrochloride, morpholine hydrochloride), etc. The amount of thecatalyst used is from 0.001 to 1 mole per 1 mole of the compound of theformula (IV).

After completion of the reaction, the desired present compounds can beobtained by the conventional after-treatments.

Of the present compounds, those represented by the following formula(I") can be produced, for example, by the following method D: ##STR12##wherein R₁, R₂, R₃, R₄, R₅, R₇ and Z are as defined above; and R"₆ is atrialkylsilyl or dialkylphenylsilyl group.

METHOD D:

A method for producing the present compounds (I") compromising reactinga compound represented by the formula (II"), ##STR13## wherein R₁, R₂,R₃, R₄, R₅, R₇ and Z are as defined above, with a trialkylsilyl chlorideor a dialkylphenylsilyl chloride.

In Method D, a solvent is usually used. For example, the followingsolvents are used: Ethers (e.g. diethyl ether, diisopropyl ether,tetrahydrofuran, dioxane), aromatic hydrocarbons (e.g. benzene,toleuen), acid amides (e.g. N,N-dimethylformamide,N,N-dimethylacetamide), sulfolane, dimethyl sulfoxide and mixtures ofthese solvents. Usually, in carrying out this reaction, a base is used.For example, the following bases are used: Alkyl lithiums (e.g. n-butyllithium), phenyl lithiums, alkyl magnesium halides (e.g. ethyl magnesiumbromide), phenyl magnesium halides, alkali metal hydrides (e.g. lithiumhydride, sodium hydride, potassium hydride). The trialkylsilyl chlorideor dialkylphenylsilyl chloride is used in an amount of from 0.1 to 10moles, preferably, from 0.5 to 2 moles per 1 mole of the compound of theformula (I"). The base is used in an amount of from 0.5 to 1.2 moles per1 mole of the compound of the formula (I"). The reaction temperature isusually from -100° to 200° C. The reaction time is usually from fiveminutes to 100 hours, preferably, from 30 minutes to 50 hours.

After completion of the reaction, the desired present compounds (I") canbe obtained by the conventional after-treatments.

Among the compounds used in Methods A, B and C, the following compoundsare novel: compounds (III), (V) and (VI); a compound (VII) representedby the formula (VII), which is included in the scope of the compound(II) for Methods A and C: ##STR14## wherein R₁, R₂, R₃ and Z are asdefined above, and R₈ is an alkyl, haloalkyl, alkenyl, haloalkenyl,alkynyl, haloalkynyl, alkoxyalkyl, alkylthioalkyl or mono ordialkylaminoalkyl group, or an optionally substituted cycloalkyl orcycloalkenyl group, or a group represented by (in which X is an oxygenor sulfur atom); and a compound represented by the formula (VIII), whichis included in the scope of the compound (IV) for Method B: ##STR15##wherein R₁, R₂, R₃, R₈ and Z are as defined above.

These compounds may be produced by the following methods.

The compound represented by the formula (III) may be produced, forexample, by reacting a compound represented by the formula (IX),##STR16## wherein R₄ and R₅ are as defined above, with a compoundrepresented by the formula (X),

    HC.tbd.C--R'.sub.6                                         (X)

wherein R'₆ is as defined above, to obtain a compound represented by theformula (XI), ##STR17## wherein R₄, R₅ and R'₆ are as defined above, andthen subjecting the resulting compound (XI) to rearrangement andhalogenation.

In carrying out the first step of this reaction, a solvent is usuallyused. The solvent used includes, ethers (e.g. diethyl ether, diisopropylether, tetrahydrofuran, dioxane), aromatic hydrocarbons (e.g. benzene,toluene), alcohols (e.g. ethylene glycol, glycerin, methanol, ethanol),amides (e.g. N,N-dimethylformamide), sulfoxides (e.g. dimethylsulfoxide, sulfolane), water and mixtures thereof. In this reaction, abase is usually used. The base used includes, alkylithiums (e.g.n-butyllithium), phenyllithiums, alkylmagnesium halides (e.g.ethylmagnesium bromide), alkali metal hydrides (e.g. lithium hydride,sodium hydride, potassium hydride), alkali metal hydroxides (e.g.lithium hydroxide, sodium hydroxide, potassium hydroxide), alkali metals(e.g. lithium, sodium, potassium), etc.

As to the amounts of the reagents used for the reaction, the amount ofthe compound of the formula (X) is from 0.1 to 10 moles, preferably,from 0.5 to 2 moles per 1 mole of the compound of the formula (IX), andthat of the base is from 0.5 to 10 moles per the same. The reactiontemperature is usually from -100° to 300° C., and the reaction time isusually from 5 minutes to 100 hours, preferably, from 30 minutes to 50hours. If necessary, a phase transfer catalyst such as ammonium salts(e.g. tetra-n-butylammonium bromide, benzyltrimethylammonium chloride),ethers (e.g. 18-Crown-6), amines [e.g. tris(3,6-dioxoheptyl)amine(TDA-1)], etc. may be used in an amount of from 0.0001 to 1 mole per 1mole of the compound of the formula (IX).

After completion of the reaction, the compound of the formula (XI) canbe obtained by the conventional after-treatments.

In the second step of the reaction to produce the compound of theformula (III) by the rearrangement and halogenation of the compound ofthe formula (XI), a solvent may not be necessary. However, when asolvent is used, a solvent such as halogenated hydrocarbons (e.g.methylene chloride, chloroform, dichloroethane), hydrocarbons (e.g.hexane, heptane), aromatic hydrocarbons (e.g. benzene, toluene,chlorobenzene), alcohols (e.g. methanol, ethanol, isopropanol), waterand mixtures thereof will usually be used. As the halogenating agentused in the reaction, hydrochloric acid, hydrobromic acid, hydroiodicacid, etc. may be used.

As to the amount of the reagent used for the reaction, the amount of thehalogenating agent is from 0.1 to 10 moles, preferably, from 0.5 to 3moles per 1 mole of the compound of the formula (XI). The reactiontemperature is usually from -30° to 200° C., preferably, from -20° to150° C.. The reaction time is usually from 5 minutes to 100 hours,preferably, from 30 minutes to 50 hours.

After completion of the reaction, the compound of the formula (III) canbe obtained by the conventional after-treatments.

The compound represented by the formula (VI) can be obtained bysubjecting the compound represented by the formula (XI) to halogenation.

In carrying out the reaction, a solvent may not be necessary. However,when a solvent is used, a solvent such as halogenated hydrocarbons (e.g.methylene chloride, chloroform, dichloroethane), hydrocarbons (e.g.hexane, heptane), aromatic hydrocarbons (e.g. benzene, toluene,chlorobenzene) and mixtures thereof may be used. As the halogenatingagent used in reaction, thionyl chloride etc. may be used.

As to the amount of the reagent used for the reaction, the amount of thehalogenating agent is from 0.1 to 10 moles, preferably, from 0.5 to 3moles per 1 mole of the compound of the formula (XI). The reactiontemperature is usually from -30° to 200° C., preferably, from -20° to150° C. The reaction time is usually from 5 minutes to 100 hours,preferably, from 30 minutes to 50 hours. If necessary a compound such asamides (e.g. N,N-dimethylformamide), pyridines (e.g. pyridine,picoline), anilines (e.g. N,N-dimethylaniline), aliphatic amines (e.g.triethylamine), etc. may be used in an amount of from 0.0001 to 1 moleper 1 mole of the compound of the formula (XI).

After completion of the reaction, the compound of the formula (VI) canbe obtained by the conventional after-treatment.

The compound represented by the formula (V) can be obtained by reactingthe compound represented by the formula (III) or (VI) with a compoundrepresented by the formula (XII),

    Y--OH                                                      (XII)

wherein Y is a group represented by ##STR18## (in which R₉ and R₁₀,which may be the same or different, are a lower alkyl or phenyl group),to obtain a compound represented by the formula (XIII), ##STR19##wherein Y, R₄, R₅ and R'₆ are as defined above, and reacting theresulting compound (XIII) with, for example, hydroxylamine or hydrazine.Alternatively, the compound (V) can be obtained by reacting theresulting compound (XIII) with, for example, a mineral acid (e.g.hydrochloric acid, sulfuric acid) and then subjecting to neutralization.

When the compound of the formula (III) or (VI) is reacted with thecompound of the formula (XII), a solvent is usually used. Such solventsinclude, for example, amides (e.g. N,N-dimethylformamide,N,N-dimethylacetamide), sulfoxides (e.g. dimethyl sulfoxide), sulfolane,aromatic hydrocarbons (e.g. benzene, toluene, chlorobenzene),halogenated hydrocarbons (e.g. methylene chloride, chloroform,dichloroethane), alcohols (e.g. methanol, ethanol, isopropanol),nitriles (e.g. acetonitrile), pyridines (e.g. pyridine, picoline), waterand mixtures thereof. When this reaction is carried out, a base isusually used. Such bases include, for example, alkali metal hydroxides(e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide), alkalimetal carbonates (e.g. potassium carbonate, sodium carbonate), alkalimetal hydrogencarbonates (e.g. sodium hydrogencarbonate), aliphaticamines (e.g. triethylamine), alkali metal alkoxides (e.g. sodiummethylate, sodium ethylate), alkali metal hydrides (e.g. sodium hydride,potassium hydride), etc.

As to the amounts of the reagents used for the reaction, the amount ofthe compound of the formula (XII) is from 0.1 to 10 moles, preferably,from 0.5 to 2 moles per 1 mole of the compound of the formula (III) or(VI), and that of the base is from 0.5 to 10 moles per the same. Thereaction temperature is usually from -30° to 200° C., preferably, from-10° to 150° C., and the reaction time is usually from 5 minutes to 100hours, preferably, from 30 minutes to 50 hours.

As an auxiliary for the reaction, for example, a phase transfer catalystsuch as ammonium salts (e.g. tetra-n-butylammonium bromide,benzyltrimethylammonium chloride), ethers (e.g. 18-Crown-6), tris(3,6-dioxoheptyl)amine (TDA-1), etc. may be used in an amount of from0.0001 to 1 mole per 1 mole of the compound of the formula (III) or(VI).

After completion of the reaction, the compound of the formula (XIII) canbe obtained by the conventional after-treatments.

When the compound of the formula (XIII) is reacted with hydroxylamine orhydrazine, or with a mineral acid (e.g. hydrochloric acid, sulfuricacid), a solvent is usually used. Such solvents include, alcohols (e.g.methanol, ethanol, isopropanol), aromatic hydrocarbons (e.g. benzene,toluene, chlorobenzene), water and mixtures thereof.

As to the amount of the reagent used for the reaction, the amount ofhydroxylamine, hydrazine or a mineral acid (e.g. hydrochloric acid,sulfuric acid) is from 0.5 to 100 moles per 1 mole of the compound ofthe formula (XIII). The reaction temperature is usually from 0° to 300°C., and the reaction time is usually from 5 minutes to 200 hours.

If necessary a phase transfer catalyst such as ammonium salts (e.g.tetra-n-butylammonium bromide, benzyltrimethylammonium chloride), ethers(e.g. 18-Crown-6), tris (3,6-dioxoheptyl)amine (TDA-1), etc. may be usedin an amount of from 0.0001 to 1 mole per 1 mole of the compound of theformula (XIII).

After completion of the reaction, the desired compound of the formula(V) can be obtained by the liquid-liquid separation of the reactionsolution, or by purification and neutralization with an acid (e.g.hydrochloric acid, sulfuric acid) or a base (e.g. sodium hydroxide,potassium hydroxide).

The compound represented by the formula (VIII) can be obtained, forexample, by reacting a compound represented by the formula (XIV),##STR20## wherein R₁, R₂ and R₃ are as defined above, with a compoundrepresented by the formula (XV),

    R.sub.8 --ZH                                               (XV)

wherein R₈ and Z are as defined above.

In carrying out this reaction, a solvent is not always necessary, butwhen a solvent is added, for example, the following solvents are used:Ethers (e.g. diethyl ether, tetrahydrofuran, dioxane), alcohols (e.g.ethylene glycol, glycerin, methanol, ethanol), acid amides (e.g.N,N-dimethylformamide, N,N-dimethylacetamide), sulfolane, dimethylsulfoxide, aromatic hydrocarbons (e.g. benzene, toluene, chlorobenzene),halogenated hydrocarbons (e.g. methylene chloride, chloroform), ketones(e.g. acetone, methyl isobutyl ketone), nitriles (e.g. acetonitrile),pyridines (e.g. pyridine, picoline), water and mixtures of thesesolvents. The compound of the formula (XV) is used in an amount of from0.5 to 10 moles per 1 mole of the compound of the formula (XIV). Thereaction temperature is usually from -20° to 200° C., preferably, from-10° to 100° C. The reaction time is usually from 5 minutes to 100hours, preferably, from 30 minutes to 50 hours.

Usually, in carrying out this reaction, the following compounds areadded as an acid-binding agent: Alkali metal hydroxides (e.g. lithiumhydroxide, sodium hydroxide, potassium hydroxide), alkali metalcarbonates (e.g. sodium carbonate, potassium carbonate), alkali metalhydrides (e.g. lithium hydride, sodium hydride, potassium hydride),alkali metals (e.g. metallic lithium, metallic sodium, metallicpotassium), alkali metal alkoxides (e.g. sodium methoxide, sodiumethoxide) and mixtures thereof. The amount of the acid-binding agentused is from 0.5 to 10 moles based on 1 mole of the compound of theformula (XIV). If necessary, as a catalyst for the reaction, a phasetransfer catalyst such as ammonium salts (e.g. tetra-n-butylammoniumbromide, benzyltrimethylammonium chloride), ethers (e.g. 18-Crown-6),amines [e.g. tris(3,6-dioxo-heptyl)amine (TDA-1)], etc. may be used inan amount of from 0.0001 to 1 mole per 1 mole of the compound of theformula (XIV).

After completion of the reaction, the desired compound of the formula(VIII) can be obtained by the conventional after-treatments.

The compound represented by the formula (VII) can be obtained byreacting the compound represented by the formula (VIII) with ahydroxylamine/acid adduct such as hydroxylamine hydrochloride,hydroxylamine sulfate, etc.

In carrying out this reaction, a solvent is not always necessary, butwhen a solvent is necessary, the following solvents are used: Ethers(e.g. diethyl ether, tetrahydrofuran, dioxane), alcohols (e.g. ethyleneglycol, glycerin, methanol, ethanol), acid amides (e.g.N,N-dimethylformamide, N,N-dimethyulacetamide), sulfolane, dimethylsulfoxide, aromatic hydrocarbons (e.g. benzene, toluene,chloro-benzene), halogenated hydrocarbons (e.g. methylene chloride,chloroform), aliphatic hydrocarbons (e.g. pentane, hexane, heptane,cyclohexane), pyridines (e.g. pyridine, picoline), acetic acid, waterand mixtures of these solvents. The hydroxylamine/acid adduct is used inan amount of from 0.5 to 10 moles per 1 mole of the compound of theformula (VIII). The reaction temperature is usually from -20° to 200°C., preferably, from -10° to 150° C. The reaction time is usually from 5minutes to 100 hours, preferably, from 5 minutes to 20 hours.

Usually, in carrying out this reaction, the following compounds can beused as an acid-binding agent: Alkali metal hydroxides (e.g. lithiumhydroxide, sodium hydroxide, potassium hydroxide), alkali metalcarbonates (e.g. sodium carbonate, potassium carbonate), alkali metalhydrides (e.g. lithium hydride, sodium hydride, potassium hydride),alkali metals (e.g. metallic lithium, metallic sodium, metallicpotassium), alkali metal alkoxides (e.g. sodium methoxide, sodiumethoxide) and mixtures thereof. The amount of the acid-binding agentused is from 0.5 to 10 moles per 1 mole of the compound of the formula(VIII). If necessary, as a catalyst for the reaction, a phase transfercatalyst such as ammonium salts (e.g. tetra-n-butylammonium bromide,benzyltrimethylammonium chloride), ethers (e.g. 18-Crown-6), amines[e.g. tris(3,6-dioxoheptyl)amine (TDA-1)], etc. may be used in an amountof from 0.0001 to 1 mole per 1 mole of the compound of the formula(VIII).

After completion of the reaction, the desired compound of the formula(VII) can be obtained by the conventional after-treatments. Thecompounds represented by the formula (XVI), (XVII) and (XVIII) ##STR21##wherein R₁, R₂, R₃, A, V, Z and n are as defined above, are described inEP No. 234,045-A2 234045A2 and JP-A-64-13086.

Examples of the present compounds represented by the formula (I) are,shown in Table 1. Of course, the present invention is not limited tothese compounds.

                                      TABLE 1                                     __________________________________________________________________________    Compounds represented by the formula:                                          ##STR22##                                                                    R.sub.1 R.sub.2 R.sub.3 R.sub.4                                                                              R.sub.5                                                                          R.sub.6     Z R.sub.7                       __________________________________________________________________________    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR23##  O                                                                                ##STR24##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR25##  O                                                                                ##STR26##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR27##  O                                                                                ##STR28##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR29##  O                                                                                ##STR30##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR31##  O                                                                                ##STR32##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR33##  O                                                                                ##STR34##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR35##  O                                                                                ##STR36##                    CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR37##  O                                                                                ##STR38##                    CH.sub.3                                                                              CH.sub.3                                                                              CH.sub.3                                                                              H      H                                                                                 ##STR39##  O                                                                                ##STR40##                    CH.sub.3                                                                              (CH.sub.2).sub.3 CH.sub.3                                                             H       H      H                                                                                 ##STR41##  O                                                                                ##STR42##                    CH.sub.3                                                                               ##STR43##                                                                            H       H      H                                                                                 ##STR44##  O                                                                                ##STR45##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR46##  O                                                                                ##STR47##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR48##  O                                                                                ##STR49##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR50##  O                                                                                ##STR51##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR52##  O                                                                                ##STR53##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR54##  S                                                                                ##STR55##                    CH.sub.3                                                                              CH.sub.3                                                                               ##STR56##                                                                            H      H                                                                                 ##STR57##  O                                                                                ##STR58##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR59##  O                                                                                ##STR60##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR61##  O                                                                                ##STR62##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR63##  S                                                                                ##STR64##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR65##  S                                                                                ##STR66##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR67##  O                                                                                ##STR68##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR69##  O                                                                                ##STR70##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  (CH.sub.2).sub.4 CH.sub.3                                                                 O                                                                                ##STR71##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR72##  S                                                                                ##STR73##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR74##  S                                                                                ##STR75##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.3                                                                         S                                                                                ##STR76##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                       S                                                                                ##STR77##                    CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR78##  S                                                                                ##STR79##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      CH.sub.3                                                                          ##STR80##  O                                                                                ##STR81##                    CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR82##  O                                                                                ##STR83##                    CH.sub.3                                                                              CH.sub.2 CH.sub.3                                                                     H       H      H                                                                                 ##STR84##  O                                                                                ##STR85##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR86##  O                                                                                ##STR87##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR88##  O                                                                                ##STR89##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.2 CH.sub.3                                                                O                                                                                ##STR90##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR91##  O                                                                                ##STR92##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR93##  O                                                                                ##STR94##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR95##  O                                                                                ##STR96##                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR97##  O                                                                                ##STR98##                    CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR99##  S                                                                                ##STR100##                   CH.sub.3                                                                              CH.sub.3                                                                              H       CH.sub.3                                                                             H                                                                                 ##STR101## O                                                                                ##STR102##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR103## O                                                                                ##STR104##                   (CH.sub.2).sub.2 CH.sub.3                                                             CH.sub.3                                                                              H       H      H                                                                                 ##STR105## O                                                                                ##STR106##                    ##STR107##                                                                           CH.sub.3                                                                              H       H      H                                                                                 ##STR108## O                                                                                ##STR109##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR110## S                                                                                ##STR111##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR112## S                                                                                ##STR113##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR114## S                                                                                ##STR115##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.3    O                                                                                ##STR116##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.3                                                                         O                                                                                ##STR117##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.2 CH.sub.3                                                                O                                                                                ##STR118##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                       O                                                                                ##STR119##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  (CH.sub.2).sub.4 CH.sub.3                                                                 O                                                                                ##STR120##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  (CH.sub.2).sub.5 CH.sub.3                                                                 O                                                                                ##STR121##                   CH.sub.3                                                                              CH.sub.3                                                                              H       CH.sub. 3                                                                            H                                                                                 ##STR122## O                                                                                ##STR123##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      CH.sub.3                                                                          ##STR124## O                                                                                ##STR125##                   CH.sub.3                                                                              CH.sub.3                                                                              H       CH.sub.3                                                                             H                                                                                 ##STR126## O                                                                                ##STR127##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR128## O                                                                                ##STR129##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR130## O                                                                                ##STR131##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR132## O                                                                                ##STR133##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR134## O                                                                                ##STR135##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR136## O                                                                                ##STR137##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR138## O                                                                                ##STR139##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR140## O                                                                                ##STR141##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR142## O                                                                                ##STR143##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR144## O                                                                                ##STR145##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR146## O                                                                                ##STR147##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR148## S                                                                                ##STR149##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR150## S                                                                                ##STR151##                    ##STR152##                                                                           CH.sub.3                                                                              H       H      H                                                                                 ##STR153## O                                                                                ##STR154##                   CH.sub.3                                                                              H       H       H      H                                                                                 ##STR155## O                                                                                ##STR156##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR157## O                                                                                ##STR158##                   CH.sub.3                                                                              (CH.sub.2).sub.2 Cl                                                                   H       H      H                                                                                 ##STR159## O                                                                                ##STR160##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  H           O                                                                                ##STR161##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR162## O                                                                                ##STR163##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H  H           O                                                                                ##STR164##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR165## O                                                                                ##STR166##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR167## O                                                                                ##STR168##                   H       CH.sub.3                                                                              H       H      H                                                                                 ##STR169## O                                                                                ##STR170##                   CH.sub.3                                                                              CH.sub.3                                                                              H       CH.sub.3                                                                             H                                                                                 ##STR171## O                                                                                ##STR172##                   CH.sub.3                                                                              CH.sub.2 CH.sub.3                                                                     H       H      H                                                                                 ##STR173## O                                                                                ##STR174##                   CH.sub.3                                                                              CH.sub.2 CH.sub.3                                                                     H       H      H                                                                                 ##STR175## O                                                                                ##STR176##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR177## O                                                                                ##STR178##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR179## O                                                                                ##STR180##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR181## O                                                                                ##STR182##                   CH.sub.3                                                                              CH.sub.3                                                                              H       CH.sub.2 CH.sub.3                                                                    H                                                                                 ##STR183## O                                                                                ##STR184##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR185## O                                                                                ##STR186##                   CH.sub.3                                                                              CH.sub.3                                                                              H                                                             n-C.sub.3 H.sub.7                                                                     H                                                                                      ##STR187##                                                                           O                                                                                     ##STR188##                                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR189## O                                                                                ##STR190##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR191## O                                                                                ##STR192##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR193## O                                                                                ##STR194##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR195## O                                                                                ##STR196##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR197## O                                                                                ##STR198##                    CH.sub.2 CH.sub.3                                                                    CH.sub.3                                                                              H       H      H                                                                                 ##STR199## O                                                                                ##STR200##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR201## O                                                                                ##STR202##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR203## O                                                                                ##STR204##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR205## O                                                                                ##STR206##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR207## O                                                                                ##STR208##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR209## O                                                                                ##STR210##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR211## O                                                                                ##STR212##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR213## O                                                                                ##STR214##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR215## O                                                                                ##STR216##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR217## O                                                                                ##STR218##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR219## O                                                                                ##STR220##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR221## O                                                                                ##STR222##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR223## O                                                                                ##STR224##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR225## O                                                                                ##STR226##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR227## O                                                                                ##STR228##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR229## O                                                                                ##STR230##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR231## O                                                                                ##STR232##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR233## O                                                                                ##STR234##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR235## O                                                                                ##STR236##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR237## O                                                                                ##STR238##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR239## O                                                                                ##STR240##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR241## O                                                                                ##STR242##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR243## O                                                                                ##STR244##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR245## O CH.sub.2 CH.sub.2                                                             CH.sub.2 CH.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR246## O CH.sub.2(CH.sub.2 )                                                           .sub.4H.sub.3                 CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR247## O                                                                                ##STR248##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR249## O CH.sub.2 CH.sub.2 F           CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR250## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR251## S                                                                                ##STR252##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR253## S                                                                                ##STR254##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR255## O                                                                                ##STR256##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR257## O                                                                                ##STR258##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR259## O                                                                                ##STR260##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR261## O                                                                                ##STR262##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR263## O                                                                                ##STR264##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR265## O                                                                                ##STR266##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR267## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR268## O                                                                                ##STR269##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR270## O                                                                                ##STR271##                   CH.sub.3                                                                              CH.sub. 3                                                                             H       H      H                                                                                 ##STR272## O                                                                                ##STR273##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR274## O                                                                                ##STR275##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR276## O                                                                                ##STR277##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR278## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR279## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR280## O                                                                                ##STR281##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR282## O                                                                                ##STR283##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR284## O                                                                                ##STR285##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR286## O CH.sub.2 CH.sub.2                                                             SCH.sub.3                     CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR287## O                                                                                ##STR288##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR289## O                                                                                ##STR290##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR291## O                                                                                ##STR292##                   CH.sub.3                                                                              CH.sub.2 F                                                                            H       H      H                                                                                 ##STR293## O                                                                                ##STR294##                   CH.sub.3                                                                              CH.sub.2 F                                                                            H       H      H                                                                                 ##STR295## O                                                                                ##STR296##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR297## O CH.sub.2 CHCHCH.sub.3         CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR298## O                                                                                ##STR299##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR300## O                                                                                ##STR301##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR302## O                                                                                ##STR303##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR304## O                                                                                ##STR305##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR306## O                                                                                ##STR307##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR308## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR309## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR310## O                                                                                ##STR311##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR312## O                                                                                ##STR313##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR314## O                                                                                ##STR315##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR316## O                                                                                ##STR317##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR318## O                                                                                ##STR319##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR320## O                                                                                ##STR321##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR322## O                                                                                ##STR323##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR324## O                                                                                ##STR325##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR326## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR327## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR328## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR329## O                                                                                ##STR330##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR331## O                                                                                ##STR332##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR333## O                                                                                ##STR334##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR335## O                                                                                ##STR336##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR337## O                                                                                ##STR338##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR339## O                                                                                ##STR340##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR341## O                                                                                ##STR342##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR343## O                                                                                ##STR344##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR345## O                                                                                ##STR346##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR347## O                                                                                ##STR348##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR349## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR350## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR351## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR352## O                                                                                ##STR353##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR354## O                                                                                ##STR355##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR356## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.2                                                             CF.sub.2 H                    CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR357## O                                                                                ##STR358##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR359## O                                                                                ##STR360##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR361## O                                                                                ##STR362##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR363## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR364## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR365## O                                                                                ##STR366##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR367## O CH.sub. 2 CF.sub.2                                                            CF.sub.2 CF.sub.3             CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR368## O                                                                                ##STR369##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR370## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR371## O                                                                                ##STR372##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR373## O                                                                                ##STR374##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR375## O                                                                                ##STR376##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR377## O CH.sub.2 CH.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR378## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR379## O                                                                                ##STR380##                   CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H       H      H                                                                                 ##STR381## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR382## O CH.sub.2 CCC.sub.2                                                            H.sub.5                       CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR383## O                                                                                ##STR384##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR385## O CH.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR386## O                                                                                ##STR387##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR388## O CH.sub.2 CH.sub.2                                                             CH.sub.2 CH.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR389## O CH.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR390## O                                                                                ##STR391##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR392## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR393## O                                                                                ##STR394##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR395## O                                                                                ##STR396##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR397## O                                                                                ##STR398##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR399## O CH.sub.2 CF.sub.2                                                             CF.sub.3                      CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR400## O CH.sub.2 CF.sub.2                                                             CF.sub.2 CF.sub.3             CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR401## O                                                                                ##STR402##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR403## O                                                                                ##STR404##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR405## O                                                                                ##STR406##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR407## O                                                                                ##STR408##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR409## O                                                                                ##STR410##                   CH.sub.3                                                                              CH.sub.3                                                                              H       H      H                                                                                 ##STR411## O                                                                                ##STR412##                   __________________________________________________________________________

When the present compounds are used as an active ingredient forinsecticidal, acaricidal and fungicidal compositions, they may be usedas they are, without adding any other ingredients. Usually, however,they are formulated into oil sprays, emulsifiable concentrates, wettablepowders, flowable concentrates, granules, dusts, aerosols, poisonousbaits, etc. by mixing with solid carriers, liquid carriers, gaseouscarriers, baits and if necessary, surface active agents and otherauxiliaries for formulation.

These formulations contain the present compounds as an active ingredientin an amount of, usually, from 0.01 to 95% by weight.

The solid carriers used in the formulation include fine powders orgranules of clays (e.g. kaolin clay, diatomaceous earth, synthetichydrated silicon dioxide, bentonite, Fubasami clay, terra abla), talcs,ceramics, other inorganic minerals (e.g. sericite, quartz, sulfur,activated carbon, calcium carbonate, hydrated silica), chemicalfertilizers (e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, urea, ammonium chloride), etc. The liquid carriers includewater, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethyl ketone), aromatic hydrocarbons (e.g. benzene, toluene, xylene,ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. hexane,cyclohexane, kerosene, gas oil), esters (e.g. ethyl acetate, butylacetate), nitriles (e.g. acetonitrile, isobutyronitrile), ethers (e.g.diisopropyl ether, dioxane), acid amides (e.g. N,N-dimethylformamide,N,N-dimethylacetamide), halogenated hydrocarbons (e.g. dichloromethane,trichloroethane, carbon tetrachloride), dimethyl sulfoxide, vegetableoils (e.g. soybean oil, cotton seed oil), etc. The gaseous carriers,i.e. propellants, include, freon gas, butane gas, LPG (liquefiedpetroleum gas), dimethyl ether, carbon dioxide gas, etc.

The surface active agents used for emulsification, dispersion, wetting,etc. include anionic surface active agents such as the salts of alkylsulfates, alkyl(aryl)sulfonates, dialkyl sulfosuccinates, the salt ofpolyoxyethylene alkylaryl ether phosphoric acid esters,naphthalenesulfonic acid/formalin condensates, etc., and nonionicsurface active agents such as polyoxyethylene alkyl ether,polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acidesters, polyoxyethylene sorbitan fatty acid esters, etc.

The auxiliaries for formulation such as fixing agents, dispersingagents, etc. include casein, gelatin, polysaccharides (e.g. starchpowder, gum arabic, cellulose derivatives, alginic acid), ligninderivatives, bentonite, saccharides, synthetic water-soluble highpolymers (e.g. polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylicacids), etc. The stabilizing agents include PAP (isopropyl acidphosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils, mineral oils, surface active agents, fatty acids andtheir esters, etc.

The base for the poisonous baits includes bait components (e.g. grainpowders, vegetable essential oils, saccharides, crystalline celluloses),antioxidants (e.g. dibutylhydroxytoluene, nordihydroguaiaretic acid),preservatives (e.g. dehydroacetic acid), attractants (e.g. cheeseperfume, onion perfume), etc. Further, red pepper powders, etc. may alsobe included as an agent for preventing children from eating the baitmistake.

The flowable formulations (water-based suspension formulations orwater-based emulsion formulations) are generally obtained by finelydispersing 1 to 75% of the active ingredient compound in watercontaining 0.5 to 15% of a dispersing agent, 0.1 to 10% of a suspensionauxiliary (e.g. protective colloids, compounds giving a thixotropicproperty) and 0 to 10% of a suitable auxiliary (e.g. defoaming agents,anticorrosives, stabilizing agents, spreading agents, penetrationauxiliaries, antifreezing agents, antibacterial agents, antimoldingagents). It is also possible to obtain oil-based suspension formulationsby replacing the water by an oil in which the active ingredientcompounds are almost insoluble. The protective colloids include,gelatin, casein, gums, cellulose ethers, polyvinyl alcohol, etc., andthe compounds giving a thixotropic property include bentonite, aluminummagnesium silicate, xanthane gum, polyacrylic acid, etc.

The formulations thus obtained are used as they are or diluted withwater, etc. Further, they may be used in mixtures with otherinsecticides, acaricides, nematocides, soil-pest controlling agents,pest-controlling agents, fungicides, herbicides, plant growthregulators, synergists, fertilizers, soil improvers, etc., or may beused simultaneously with these chemicals without mixing.

When the present compounds are used as active ingredients foragricultural insecticidal and acaricidal compositions, the dosage rateof the active ingredient is usually from 1 to 1,000 g/10 ares. When theemulsifiable concentrates, wettable powders, flowable concentrates, etc.are used in dilution with water, the application concentration of theactive ingredient is from 10 to 1,000 ppm. The granules, dusts, etc. areused as they are without being diluted. When the present compounds areused as household and public hygienic insecticidal and acaricidalcompositions, the emulsifiable concentrates, wettable powders, flowableconcentrates, etc. are applied diluted with water to from 10 to 1,000ppm, and the oil sprays, aerosols, poisonous baits, etc. are applied asthey are.

When the present compounds are used as active ingredients for fungicidalcompositions the dosage rate of the active ingredient is usually from 1to 1,000 g/10 ares. When the emulsifiable concentrates, wettablepowders, flowable concentrates, etc. are used in dilution with water,the application concentration of the active ingredient is from 10 to100,000 ppm. The granules, dusts, etc. are used as they are withoutbeing diluted.

The present compounds are also used as seed disinfectants.

Although any of these dosage rates and application concentrations mayvary with the kind of formulations, when, where and how theseformulations are applied, the kind of pests, the degree of damage, etc.,they may be increased or decreased independently of the ranges explainedabove.

The present invention will be illustrated in more detail with referenceto the following production examples, formulation examples and testexamples, but it is not limited to these examples.

First, the production examples will be shown.

PRODUCTION EXAMPLE 1 (Method A)

One gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximewas added to 10 ml of an N,N-dimethylfomamide solution containing 0.11 g(0.0046 mole) of sodium hydride, and the mixture was stirred at roomtemperature for 3 hours. Thereafter, 1.53 g (0.007 mole) of1-bromo-2fluoro-6,6-dimethylhept-2-ene-4-yne was added underice-cooling, and the mixture was stirred at room temperature for 3hours. The reaction mixture was poured into 100 ml of ice water andextracted with three 50-ml portions of ethyl acetate. The organic layerswere combined, washed once with 100 ml of a saturated aqueous sodiumchloride solution and concentrated under reduced pressure. The residuewas subjected to column chromatography on silica gel to obtain 0.36 g of1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

m.p. 57°-58° C.

PRODUCTION EXAMPLE 2 (Method C)

One gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximewas added to 10 ml of an N,N-dimethylformamide solution containing 0.11g (0.0046 mole) of sodium hydride, and the mixture was stirred at roomtemperature for 3 hours. Thereafter, 0.89 g (0.0052 mole) of3-chloro-6,6-dimethyl-6methoxyhex-1-ene-4-yne was added underice-cooling, and the mixture was stirred at room temperature for 3hours. The reaction mixture was poured into 100 ml of ice water andextracted with three 50-ml portions of ethyl acetate. The organic layerswere combined, washed once with 100 ml of a saturated aqueous sodiumchloride solution and concentrated under reduced pressure. The residuewas subjected to column chromatography on silica gel to obtain 0.21 g of1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethyl-6-methoxyhex-2-ene-4-ynyl ether.

n_(D) ²⁴.5 1.5331.

PRODUCTION EXAMPLE 3 (Method A)

One gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximewas added to 10 ml of an N,N-dimethylformamide solution containing 0.11g (0.0046 mole) of sodium hydride, and the mixture was stirred at roomtemperature for 3 hours. Thereafter, 0.61 g (0.0052 mole) of1-chloro-2-fluoropent-2-ene-4-yne was added under ice-cooling, and themixture was stirred at room temperature for 3 hours. The reactionmixture was poured into 100 ml of ice water and extracted with three50-ml portions of ethyl acetate. The organic layers were combined,washed once with 100 ml of a saturated aqueous sodium chloride solutionand concentrated under reduced pressure. The residue was subjected tocolumn chromatography on silica gel to obtain 0.31 g of1,3-dimethyl-5-phenoxypyrazol-4-carboaldoximeO-2-fluoropent-2-ene-4-ynyl ether.

n_(D) ²⁵.5 1.5492.

PRODUCTION EXAMPLE 4 (Method A)

One gram (0.0042 mole) of1,3-dimethyl-5-cyclohexyloxypyrazol-4-carboaldoxime was added to 10 mlof an N,N-dimethylformamide solution containing 0.11 g (0.0046 mole) ofsodium hydride, and the mixture was stirred at room temperature for 3hours. Thereafter, 1.1 g (0.005 mole) of1-bromo-2-fluoro-6,6-dimethylhept-2-ene-4-yne was added underice-cooling, and the mixture was stirred at room temperature for 3hours. The reaction mixture was poured into 100 ml of ice water andextracted with three 50-ml portions of ethyl acetate. The organic layerswere combined, washed once with 100 ml of a saturated aqueous sodiumchloride solution and concentrated under reduced pressure. The residuewas subjected to column chromatography on silica gel to obtain 0.27 g of1,3-dimethyl-5-cyclohexyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

n_(D) ²⁵.0 1.5159.

PRODUCTION EXAMPLE 5 (Method A)

One gram (0.0035 mole) of1,3-dimethyl-5-(2,2,3,3,3-pentafluoro)propyloxypyrazol-4-carboaldoximewas added to 10 ml of an N,N-dimethylformamide solution containing 92 mg(0.0038 mole) of sodium hydride, and the mixture was stirred at roomtemperature for 3 hours. Thereafter, 0.92 g (0.0042 mole) of1-bromo-2-fluoro-6,6-dimethylhept-2-ene-4-yne was added underice-cooling, and the mixture was stirred at room temperature for 3hours. The reaction mixture was poured into 100 ml of ice water andextracted with three 50-ml portions of ethyl acetate. The organic layerswere combined, washed once with 100 ml of a saturated aqueous sodiumchloride solution and concentrated under reduced pressure. The residuewas subjected to column chromatography on silica gel to obtain 0.31 g of1,3-dimethyl-5-(2,2,3,3,3-pentafluoro)propyloxypyrazol-4-carboaldoximeO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

n_(D) ²³.0 1.4561.

PRODUCTION EXAMPLE 6 (Method B)

One gram (0.0040 mole) of1,3-dimethyl-5-(p-chlorophenoxy)pyrazol-4-carboaldehyde was dissolved in10 ml of methanol', 0.75 g (0.0044 mole) of2-fluoro-6,6-dimethylhept-2-ene-4-ynyloxyamine was added to theresulting solution. Thereafter, a catalytic amount of a hydrogenchloride gas was bubbled into the reaction solution, and the reactionmixture was aged overnight at room temperature. The reaction mixture waspoured into 100 ml of ice water and extracted with three 50-ml portionsof ethyl acetate. The organic layers were combined, washed once with 100ml of a saturated aqueous sodium chloride solution and concentratedunder reduced pressure. The residue was subjected to columnchromatography on silica gel to obtain 0.23 g of1,3-dimethyl-5-(p-chlorophenoxy)pyrazol-4-carboaldehydeoximeO-2-fluoro-6,6-dimethyl-hept-2-ene-4-ynyl ether.

n_(D) ²⁶.0 1.5431.

PRODUCTION EXAMPLE 7 (Method D)

0.5 grams (0.0017 mole) of1,3-dimethyl-5-phenoxypyrazol-4-carboaldehydeoximeO-2-fluoropenta-2-ene-4-yne was dissolved in 10 ml of anhydroustetrahydrofurane. 1.13 ml of 1.5M hexane solution of n-butyllithium wasadded to the resulting solution at -60° C. at -60° C. or less undercooling in a dry ice-acetone bath. The reaction mixture was aged for 30minutes at -60° C. or less. Thereafter, 0.22 g (0.002 mole) oftrimethylsilylchloride was added at -60° C. or less. The reactionsolution was aged overnight and then was poured into 100 ml of ice waterand extracted with three 50 ml portions of ethyl acetate. The organiclayers were combined, washed once with 100 ml of a saturated aqueoussodium chloride solution and concentrated under reduced pressure. Theresidue was subjected to column chromatography on silica gel to obtain0.13 g of 1,3-dimethyl-5-phenoxypyrazol-4-carboaldehydeoximeO-2-fluoro-5-trimethylsilylpenta-2-ene-4-ynyl ether.

n_(D) ²⁵.0 1.5239.

Some of the present compounds thus obtained are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Compounds represented by the formula                                           ##STR413##                                                                   Compound                                                 Physical             No.   R.sub.1                                                                             R.sub.2                                                                             R.sub.3                                                                          R.sub.4                                                                             R.sub.5                                                                          R.sub.6    Z R.sub.7       Properties           __________________________________________________________________________     (1)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR414##                                                                              O                                                                                ##STR415##   m.p. 57-58.degree                                                             . C.                  (2)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR416##                                                                              O                                                                                ##STR417##    m.p. 73-74.degre                                                             e. C.                 (3)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR418##                                                                              O                                                                                ##STR419##   n.sub.D.sup.28.0                                                              .5285                 (4)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR420##                                                                              O                                                                                ##STR421##   n.sub.D.sup.27.5                                                              .5288                 (5)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR422##                                                                              O                                                                                ##STR423##   n.sub.D.sup.28.0                                                              .5431                 (6)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR424##                                                                              O                                                                                ##STR425##   n.sub.D.sup.26.5                                                              .5332                 (7)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR426##                                                                              O                                                                                ##STR427##   n.sub.D.sup.                                                                  26.0 1.5395           (8)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR428##                                                                              O                                                                                ##STR429##   m.p. 91.4°                                                              C.                   (9)  CH.sub.3                                                                            CH.sub.3                                                                            CH.sub.3                                                                         H     H                                                                                 ##STR430##                                                                              O                                                                                ##STR431##   m.p. 117.2.degree                                                             . C.                 (10)  CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                   H  H     H                                                                                 ##STR432##                                                                              O                                                                                ##STR433##   n.sub.D.sup.29.0                                                              .5355                (11)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR434##                                                                              S                                                                                ##STR435##   m.p. 95.5°                                                              C.                  (12)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR436##                                                                              S                                                                                ##STR437##   m.p. 95.3°                                                              C.                  (13)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR438##                                                                              S                                                                                ##STR439##   n.sub.D.sup.25.0                                                              .5727                (14)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR440##                                                                              O                                                                                ##STR441##   n.sub.D.sup.28.0                                                              .5378                (15)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR442##                                                                              O                                                                                ##STR443##   n.sub.D.sup.28.0                                                              .5425                (16)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                  n-C.sub.6 H.sub.13                                                                  O                                                                                    ##STR444##                                                                         n.sub.D.sup.28.0 1.5322                                     (17)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR445##                                                                              O                                                                                ##STR446##   m.p. 71.8°                                                              C.                  (18)  CH.sub.3                                                                            CH.sub.3                                                                            H                                                           n-C.sub.3 H.sub.7                                                                   H                                                                                    ##STR447##                                                                         O                                                                                 ##STR448##                                                                         n.sub.D.sup.28.0 1.5247                            (19)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR449##                                                                              O                                                                                ##STR450##   n.sub.D.sup.26.3                                                              .5091                (20)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR451##                                                                              O                                                                                ##STR452##   n.sub.D.sup.24.5                                                              .5451                (21)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR453##                                                                              O                                                                                ##STR454##   n.sub.D.sup.25.5                                                              .5392                (22)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR455##                                                                              O                                                                                ##STR456##   n.sub.D.sup.23.0                                                              .5462                (23)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR457##                                                                              O                                                                                ##STR458##   n.sub.D.sup.23.0                                                              .5391                (24)  CH.sub.3                                                                            CH.sub.3                                                                            H  CH.sub.2 CH.sub.3                                                                   H                                                                                 ##STR459##                                                                              O                                                                                ##STR460##   n.sub.D.sup.24.0                                                              .5248                (25)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR461##                                                                              O                                                                                ##STR462##   n.sub.D.sup.22.0                                                              .5459                (26)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR463##                                                                              O                                                                                ##STR464##   n.sub.D.sup.22.0                                                              .5295                (27)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR465##                                                                              O                                                                                ##STR466##   n.sub.D.sup.23.0                                                              .5051                (28)  CH.sub.3                                                                            CH.sub.3                                                                            H  CH.sub.3                                                                            H                                                                                 ##STR467##                                                                              O                                                                                ##STR468##   n.sub.D.sup.25.0                                                              .5298                (29)  CH.sub.3                                                                            CH.sub.3                                                                            H  CH.sub.3                                                                            H                                                                                 ##STR469##                                                                              O                                                                                ##STR470##   n.sub.D.sup.21.0                                                              .5305                (30)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR471##                                                                              O                                                                                ##STR472##   n.sub.D.sup.23.0                                                              .5425                (31)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR473##                                                                              O                                                                                ##STR474##   n.sub.D.sup.19.1                                                              .5381                (32)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR475##                                                                              O                                                                                ##STR476##   n.sub.D.sup.25.0                                                              .5342                (33)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR477##                                                                              O                                                                                ##STR478##   n.sub.D.sup.25.0                                                              .5329                (34)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR479##                                                                              O                                                                                ##STR480##   n.sub.D.sup.24.7                                                              .5369                (35)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR481##                                                                              O                                                                                ##STR482##   n.sub.D.sup.24.5                                                              .5331                (36)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR483##                                                                              O                                                                                ##STR484##   n.sub.D.sup.25.0                                                              .5159                (37)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR485##                                                                              O                                                                                ##STR486##   n.sub.D.sup.24.0                                                              .5189                (38)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR487##                                                                              O                                                                                ##STR488##   n.sub.D.sup.25.0                                                              1.5130               (39)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR489##                                                                              O                                                                                ##STR490##   n.sub.D.sup.24.7                                                              .5112                (40)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR491##                                                                              O                                                                                ##STR492##   n.sub.D.sup.26.6                                                              .5150                (41)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR493##                                                                              O                                                                                ##STR494##   n.sub.D.sup.22.0                                                              .5055                (42)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR495##                                                                              O                                                                                ##STR496##   n.sub.D.sup.25.5                                                              .5061                (43)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR497##                                                                              O CH.sub.2 CH.sub.2 CH.sub.2                                                    CH.sub.3      n.sub.D.sup.24.0                                                              .5049                (44)  CH.sub. 3                                                                           CH.sub.3                                                                            H  H     H                                                                                 ##STR498##                                                                              O (CH.sub.2).sub.5 CH.sub.3                                                                   n.sub.D.sup.24.0                                                              .5005                (45)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR499##                                                                              O                                                                                ##STR500##   n.sub.D.sup.24.0                                                              .4973                (46)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR501##                                                                              O CH.sub.2 CH.sub.2 F                                                                         n.sub.D.sup.22.0                                                              .5065                (47)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR502##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.21.0                                                              .5305                (48)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR503##                                                                              S                                                                                ##STR504##   n.sub.D.sup.25.0                                                              .5285                (49)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR505##                                                                              S                                                                                ##STR506##   n.sub.D.sup.21.0                                                              .5290                (50)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR507##                                                                              O                                                                                ##STR508##   n.sub.D.sup.24.5                                                              .5325                (51)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR509##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.22.0                                                              .4812                (52)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR510##                                                                              O                                                                                ##STR511##   n.sub.D.sup.24.5                                                              .5574                (53)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR512##                                                                              O CH.sub.2 CCC.sub.2 H.sub.5                                                                  n.sub.D.sup.25.0                                                              .5162                (54)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR513##                                                                              O                                                                                ##STR514##   n.sub.D.sup.25.5                                                              .5035                (55)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR515##                                                                              O CH.sub.3      n.sub.D.sup.24.0                                                              .5120                (56)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR516##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.23.0                                                              .4561                (57)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR517##                                                                              O                                                                                ##STR518##   n.sub.D.sup.25.0                                                              .5128                (58)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR519##                                                                              O                                                                                ##STR520##   n.sub.D.sup.24.0                                                              .5308                (59)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR521##                                                                              O                                                                                ##STR522##   n.sub.D.sup.24.0                                                              .5368                (60)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR523##                                                                              O                                                                                ##STR524##   n.sub.D.sup.23.0                                                              .5201                (61)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR525##                                                                              O CH.sub.2 CH.sub.2 CF.sub.3                                                                  n.sub.D.sup.23.5                                                              .4685                (62)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR526##                                                                              O CH.sub.2 CF.sub.2 CF.sub.2                                                    CF.sub.3      n.sub.D.sup.24.5                                                              .4602                (63)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR527##                                                                              O                                                                                ##STR528##   n.sub.D.sup.25.0                                                              .5476                (64)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR529##                                                                              O                                                                                ##STR530##   n.sub.D.sup.23.5                                                              .5457                (65)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR531##                                                                              O                                                                                ##STR532##   n.sub.D.sup.25.0                                                              .5569                (66)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR533##                                                                              O                                                                                ##STR534##   n.sub.D.sup.24.5                                                              .5548                (67)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR535##                                                                              O                                                                                ##STR536##   n.sub.D.sup.23.0                                                              .5561                (68)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR537##                                                                              O                                                                                ##STR538##   n.sub.D.sup.24.5                                                              .5285                (69)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR539##                                                                              O                                                                                ##STR540##   n.sub.D.sup.23.5                                                              .5234                (70)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR541##                                                                              O                                                                                ##STR542##   n.sub.D.sup.23.5                                                              .5265                (71)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR543##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.22.0                                                              .5059                (72)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR544##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.25.0                                                              .4985                (73)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR545##                                                                              O CH.sub.2 CF.sub.2 CF.sub.2                                                    CF.sub.3      n.sub.D.sup.24.0                                                              .4913                (74)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR546##                                                                              O                                                                                ##STR547##   n.sub.D.sup.23.5                                                              .4906                (75)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR548##                                                                              O                                                                                ##STR549##   n.sub.D.sup.23.0                                                              .5258                (76)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR550##                                                                              O                                                                                ##STR551##   n.sub.D.sup.25.0                                                              .5326                (77)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR552##                                                                              O                                                                                ##STR553##   n.sub.D.sup.24.5                                                              .5318                (78)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR554##                                                                              O                                                                                ##STR555##   n.sub.D.sup.23.0                                                              .5251                (79)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR556##                                                                              O                                                                                ##STR557##   n.sub.D.sup.24.0                                                              .5385                (80)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR558##                                                                              O                                                                                ##STR559##   n.sub.D.sup.24.5                                                              .5301                (81)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR560##                                                                              O                                                                                ##STR561##   n.sub.D.sup.25.0                                                              .5083                (82)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR562##                                                                              O                                                                                ##STR563##   n.sub.D.sup.24.0                                                              .5162                (83)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR564##                                                                              O                                                                                ##STR565##   n.sub.D.sup.23.0                                                              .5157                (84)  CH.sub.3                                                                            CH.sub. 3                                                                           H  H     H                                                                                 ##STR566##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.23.0                                                              .4808                (85)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR567##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.24.0                                                              .4752                (86)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR568##                                                                              O CH.sub.2 CF.sub.2 CF.sub.2                                                    CF.sub.3      n.sub.D.sup.24.5                                                              .4649                (87)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR569##                                                                              O                                                                                ##STR570##   n.sub.D.sup.23.0                                                              .4763                (88)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR571##                                                                              O                                                                                ##STR572##   n.sub.D.sup.25.0                                                              .4511                (89)  CH.sub.3                                                                            CH.sub. 3                                                                           H  H     H                                                                                 ##STR573##                                                                              O CH.sub.2 CF.sub.2 CF.sub.2                                                    CF.sub.2 CF.sub.2 H                                                                         n.sub.D.sup.25.0                                                              .4578                (90)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR574##                                                                              O                                                                                ##STR575##   n.sub.D.sup.23.5                                                              .5317                (91)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR576##                                                                              O                                                                                ##STR577##   n.sub.D.sup.23.5                                                              .5308                (92)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR578##                                                                              O                                                                                ##STR579##   n.sub.D.sup.23.0                                                              .5295                (93)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR580##                                                                              O                                                                                ##STR581##   n.sub.D.sup.24.5                                                              .5316                (94)  CH.sub.2 CH.sub.3                                                                   CH.sub. 3                                                                           H  H     H                                                                                 ##STR582##                                                                              O                                                                                ##STR583##   n.sub.D.sup.25.0                                                              .5345                (95)  CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR584##                                                                              O                                                                                ##STR585##   n.sub.D.sup.24.5                                                              .5326                (96)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR586##                                                                              O                                                                                ##STR587##   n.sub.D.sup.24.0                                                              .5311                (97)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR588##                                                                              O                                                                                ##STR589##   n.sub.D.sup.23.5                                                              .5314                (98)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR590##                                                                              O                                                                                ##STR591##   n.sub.D.sup.24.0                                                              .5323                (99)  CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR592##                                                                              O                                                                                ##STR593##   n.sub.D.sup.24.0                                                              .5318                (100) CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR594##                                                                              O                                                                                ##STR595##   n.sub.D.sup.23.0                                                              .5293                (101) CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR596##                                                                              O                                                                                ##STR597##   n.sub.D.sup.23.5                                                              .5335                (102) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR598##                                                                              O                                                                                ##STR599##   n.sub.D.sup.24.5                                                              .5163                (103) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR600##                                                                              O                                                                                ##STR601##   n.sub.D.sup.25.0                                                              .5172                (104) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR602##                                                                              O                                                                                ##STR603##   n.sub.D.sup.23.0                                                              .5081                (105) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR604##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.22.5                                                              .4823                (106) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR605##                                                                              O                                                                                ##STR606##   n.sub.D.sup.23.5                                                              .4786                (107) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR607##                                                                              O CH.sub.2 CF.sub.2 CF.sub.2                                                    CF.sub.3      n.sub.D.sup.23.5                                                              .4762                (108) CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR608##                                                                              O                                                                                ##STR609##   n.sub.D.sup.23.5                                                              .5166                (109) CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR610##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.22.0                                                              .4803                (110) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR611##                                                                              O                                                                                ##STR612##   n.sub.D.sup.24.5                                                              .5125                (111) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR613##                                                                              O                                                                                ##STR614##   n.sub.D.sup.24.0                                                              .5204                (112) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR615##                                                                              O                                                                                ##STR616##   n.sub.D.sup.25.5                                                              .5089                (113) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR617##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.23.5                                                              .4872                (114) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR618##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.24.0                                                              .4712                (115)  CH.sub.2 CH.sub.3                                                                  CH.sub.3                                                                            H  H     H                                                                                 ##STR619##                                                                              O                                                                                ##STR620##   n.sub.D.sup.24.0                                                              .5159                (116) CH.sub.2 CH.sub.3                                                                   CH.sub.3                                                                            H  H     H                                                                                 ##STR621##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.24.5                                                              .4805                (117) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H  H          O                                                                                ##STR622##   n.sub.D.sup.25.5                                                              .5492                (118) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H  H          O                                                                                ##STR623##   n.sub.D.sup.24.0                                                              .5413                (119) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR624##                                                                              O                                                                                ##STR625##   n.sub.D.sup.22.0                                                              .5365                (120) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR626##                                                                              O                                                                                ##STR627##   n.sub.D.sup.25.5                                                              .5600                (121) CH.sub.3                                                                            CH.sub. 3                                                                           H  H     H                                                                                 ##STR628##                                                                              O                                                                                ##STR629##   n.sub.D.sup.25.5                                                              .5621                (122) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR630##                                                                              O                                                                                ##STR631##   n.sub.D.sup.25.0                                                              .5485                (123) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR632##                                                                              O                                                                                ##STR633##   n.sub.D.sup.24.0                                                              .6003                (124) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR634##                                                                              O                                                                                ##STR635##   n.sub.D.sup.24.0                                                              .5997                (125) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR636##                                                                              O                                                                                ##STR637##   n.sub.D.sup.22.5                                                              .5973                (126) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR638##                                                                              O                                                                                ##STR639##   n.sub.D.sup.22.5                                                              .6012                (127) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR640##                                                                              O                                                                                ##STR641##   n.sub.D.sup.23.0                                                              .5790                (128) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR642##                                                                              O CH.sub.2 CF.sub.2 CF.sub.3                                                                  n.sub.D.sup.24                                                                1.5356               (129) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR643##                                                                              O                                                                                ##STR644##   n.sub.D.sup.24.0                                                              .5192                (130) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR645##                                                                              O CH.sub.2 CH.sub.2 CH.sub.2                                                    CH.sub.3      n.sub.D.sup.23.6                                                              .5181                (131) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR646##                                                                              O CH.sub.2 CF.sub.3                                                                           n.sub.D.sup.22.5                                                              .4745                (132) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR647##                                                                              O                                                                                ##STR648##   n.sub.D.sup.22.5                                                              .5189                (133) CH.sub.3                                                                            CH.sub.3                                                                            H  H     H                                                                                 ##STR649##                                                                              O  CH.sub.2 CF.sub.2 CF.sub.3                                                                 n.sub.D.sup.25.0                                                              .4891                __________________________________________________________________________

PRODUCTION EXAMPLE 8 (Production of the Intermediate)

Ten grams (0.122 mole) of 3,3-dimethyl-1-butyne was dissolved in 100 mlof anhydrous tetrahydrofuran, and the resulting solution was cooled to-40° C. or less in a dry ice-acetone bath. Under a stream of a nitrogengas, 81.13 ml of a 1.5M hexane solution of n-butyllithium was addeddropwise at -40° C. or less with stirring. After aging ageing thereaction solution at -50° C. for 30 minutes, 9.01 g (0.122 mole) of2-fluoroacrolein was added dropwise at -50° C. or less. After thereaction mixture was allowed to stand overnight at room temperature, itwas poured into 200 ml of ice water and extracted with two 100-mlportions of ethyl acetate. The organic layers were combined, washed oncewith 100 ml of a saturated aqueous sodium chloride solution andconcentrated under reduced pressure. The resulting oily product wasdistilled under reduced pressure to obtain 11 g of2-fluoro-3-hydroxy-6,6-dimethylhept- 1-ene-4-yne (bp₂₀, 86° C.).

PRODUCTION EXAMPLE 9 (Production of the Intermediate)

Ten grams (0.102 mole) of 3,3-dimethyl-3-methoxy-1-propyne, producedaccording to the method described in Zh. Org. Khim., 2(11), 1969-1973(1966), was dissolved in 100 ml of anhydrous tetrahydrofuran, and theresulting solution was cooled to -40° C. or less in a dry ice-acetonebath. Under a stream of a nitrogen gas, 68 ml of 1.5M hexane solution ofn-butyllithium was added dropwise at -40° C. or less with stirring.After aging the reaction solution at -50° C. for 30 minutes, 7.53 g(0.102 mole) of 2-fluoroacrolein was added dropwise at -50° C. or less.After the reaction mixture was allowed to stand overnight at roomtemperature, it was poured into 200 ml of ice water and extracted withtwo 100-ml portions of ethyl acetate. The organic layers were combined,washed once with 100 ml of a saturated aqueous sodium chloride solutionand concentrated under reduced pressure. The residue was distilled underreduced pressure to obtain 3 g of2-fluoro-3-hydroxy-6,6-dimethyl-6-methoxyhex-1-ene-4-yne.

n_(D) ²³.0 1.4912.

Thus, compounds of the formula (XI) shown in Table 3 can be obtained ina similar manner.

                  TABLE 3                                                         ______________________________________                                        Compounds represented by the formula:                                          ##STR650##                                                                   R.sub.4 R.sub.5                                                                             R.sub.6 '       Physical properties                             ______________________________________                                        H       H                                                                                    ##STR651##     n.sub.D.sup.25.0 1.4516                         H       H                                                                                    ##STR652##     n.sub.D.sup.24.0 1.4438                         H       H                                                                                    ##STR653##     n.sub.D.sup.23.5 1.4751                         H       H                                                                                    ##STR654##     bp.sub.20 144-146° C.                    H       H                                                                                    ##STR655##                                                     H       H                                                                                    ##STR656##                                                     ______________________________________                                    

PRODUCTION EXAMPLE 10 (Production of the intermediate)

Ten grams (0.064 mole) of2-fluoro-3-hydroxy-6,6-dimethylhept-1-ene-4-yne was added 200 ml ofconcentrated hydrochloric acid, and the mixture was aged for 5 hours atroom temperature with stirring. The reaction mixture was extracted withthree 100 ml portions of diethylether. The organic layers were combined,washed once with 100 ml of a saturated aqueous sodium chloride solutionand concentrated under reduced pressure. The resulting oily product wasdistilled under reduced pressure to obtain 5 g of1-chloro-2-fluoro-6,6-dimethylhept-2-ene-4-yne.

bp₁₈ 86°-88° C.

Thus, compounds of the formula (III) shown in Table 4 can be obtained ina similar manner.

                  TABLE 4                                                         ______________________________________                                        Compounds represented by the formula:                                          ##STR657##                                                                                                      Physical                                   R.sub.4                                                                              R.sub.5                                                                             R.sub.6 '      W.sub.1                                                                              properties                                 ______________________________________                                        H      H                                                                                    ##STR658##    Br     n.sub.D.sup.24.4 1.4979                    H      H                                                                                    ##STR659##    Cl     n.sub.D.sup.25.0 1.4803                    H      H                                                                                    ##STR660##    Cl     n.sub.D.sup.24.0 1.4786                    H      H                                                                                    ##STR661##    Cl                                                H      H                                                                                    ##STR662##    Cl     n.sub.D.sup.24.0 1.5062                    H      H                                                                                    ##STR663##    Cl     n.sub.D.sup.23.0 1.4717                    ______________________________________                                    

PRODUCTION EXAMPLE 11 (Production of the intermediate)

Ten grams (0.064 mole) of2-fluoro-3-hydroxy-6,6-dimethylhept-1-ene-4-yne was dissolved in 100 mlof hexane, and to 50 mg (6.8×10⁻⁴ mole) of N,N-dimethylformamide and11.42 g (0.095 mole) of thionyl chloride were added to the resultingsolution. The mixture was reacted overnight at room temperature withstirring with a hydrogen chloride gas trap mounted on the reactor. Thereaction mixture was concentrated under reduced pressure. The resultingoily product was distilled under reduced pressure to obtain 10.1 g of2-fluoro-3-chloro-6,6-dimethylhept-1-ene-4-yne.

bp₄₀ 78°-82° C.

Thus, compounds of the formula (VI) shown in Table 5 can be obtained ina similar manner.

                  TABLE 5                                                         ______________________________________                                        Compounds represented by the formula:                                          ##STR664##                                                                                                      Physical                                   R.sub.4                                                                              R.sub.5                                                                             R.sub.6 '      W.sub.2                                                                              properties                                 ______________________________________                                        H      H                                                                                    ##STR665##    Cl     n.sub.D.sup.24.0 1.4759                    H      H                                                                                    ##STR666##    Cl     n.sub.D.sup.25.0 1.4811                    H      H                                                                                    ##STR667##    Cl                                                H      H                                                                                    ##STR668##    Cl                                                H      H                                                                                    ##STR669##    Cl     n.sub.D.sup.24.5 1.4810                    H      H                                                                                    ##STR670##    Cl     n.sub.D.sup.23.5 1.4734                    ______________________________________                                    

PRODUCTION EXAMPLE 12 (Production of the intermediate)

1.87 grams (0.0115 mole) of N-hydroxyphthalimide was dissolved in 20 mlof N,N-dimethylformamide, and 2 g (0.0115 mole) of1-chloro-2-fluoro-6,6-dimethylhept-2-ene-4-yne and 1.27 g (0.0127 mole)of triethylamine were added to the resulting solution. The mixture wasreacted at 60° C. for 5 hours with stirring. The reaction mixture wasthen poured into 200 ml of ice water and extracted with two 100-mlportions of ethyl acetate. The organic layers were combined, washed oncewith 100 ml of a saturated aqueous sodium chloride solution andconcentrated under reduced pressure. The residue was subjected to columnchromatography on silica gel to obtain 0.7 g of hydroxyphthalimideO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

0.5 gram (1.7×10⁻³ mole) of N-hydroxyphthalimideO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether was dissolved in 10 ml oftoluene, and 0.24 g (3.4×10⁻³ mole) of hydroxylamine hydrochloride, 10ml of water and 28 mg (8.5×10⁵ mole) of tetra-n-butylammonium bromidewas added to the resulting mixture. The reaction mixture was violentlystirred, and 4.1 ml of a 0.5% aqueous sodium hydroxide solution wasadded dropwise at room temperature. After aging the solution at roomtemperature for 10 hours with stirring, the solution was separated intotwo layers. The aqueous layer was extracted once with 50 ml of toluene.The organic layers were combined and washed with 50 ml of a saturatedaqueous sodium chloride solution. The organic layer was concentratedunder reduced pressure to obtain 0.1 g of hydroxylamineO-2-fluoro-6,6-dimethylhept-2-ene-4-ynyl ether.

n_(D) ²⁴ 1.5116.

Thus, compounds of the formula (V) shown in Table 6 can be obtained in asimilar manner.

                  TABLE 6                                                         ______________________________________                                        Compounds represented by the formula:                                          ##STR671##                                                                                                    Physical                                     R.sub.4  R.sub.5                                                                             R.sub.6 '         properties                                   ______________________________________                                        H        H                                                                                    ##STR672##       n.sub.D.sup.24.5 1.4911                      H        H                                                                                    ##STR673##       n.sub.D.sup.23.5 1.4832                      H        H                                                                                    ##STR674##       n.sub.D.sup.23.0 1.5193                      H        H                                                                                    ##STR675##                                                    H        H                                                                                    ##STR676##                                                    H        H                                                                                    ##STR677##       n.sub.D.sup.25.0 1.4863                      ______________________________________                                    

The formulation examples will be shown below.

FORMULATION EXAMPLE 1 (Emulsifiable concentrate)

Ten parts of each of the compounds (1) to (133) are dissolved in amixture of 35 parts of xylene and 35 parts of dimethylformamide, and 14parts of polyoxyethylene styrylphenyl ether and 6 parts of calciumdodecylbenzenesulfonate are added to the resulting solution. Theresulting mixture is well mixed with stirring to obtain a 10%emulsifiable concentrate of each compound.

FORMULATION EXAMPLE 2 (Wettable powder)

Twenty parts of each of the compounds (1) to (133) are added to amixture of 4 parts of sodium lauryl sulfate, 2 parts of calciumlignosulfonate, 20 parts of synthetic hydrated silicon dioxide finepowders and 54 parts of diatomaceous earth. The resulting mixture iswell mixed with stirring by a juice mixer to obtain a 20% wettablepowder of each compound.

FORMULATION EXAMPLE 3 (Granule)

To 5 parts of each of the compounds (1), (2), (8), (9), (11), (12) and(17) are added 5 parts of synthetic hydrated silicon dioxide finepowders, 5 parts of sodium dodecylbenzenesulfonate, 30 parts ofbentonite and 55 parts of clay, and the resulting mixture is well mixedwith stirring. Thereafter, a suitable amount of water is added, and themixture is further stirred, granulated on a granulator and air-dried toobtain a 5% granule of each compound.

FORMULATION EXAMPLE 4 (Dust)

One part of each of the compounds (1) to (133) is dissolved in asuitable amount of acetone, and 5 parts of synthetic hydrated silicondioxide fine powders, 0.3 part of PAP and 93.7 parts of clay are addedto resulting mixture. The mixture is well mixed with stirring on a juicemixer, and acetone is removed by vaporization to obtain a 1% dust ofeach compound.

FORMUATION EXAMPLE 5 (Flowable concentrate)

Twenty parts of each of the compounds (1), (2), (8), (9), (11), (12) and(17) and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of anaqueous solution containing 2 parts of polyvinyl alcohol. The resultingmixture is finely pulverized on a sand grinder to a particle size of 3μor less. 40 parts of an aqueous solution containing 0.05 part ofxanthane gum and 0.1 part of aluminum magnesium silicate and then 10parts of propylene glycol are added to the resulting mixture. Themixture is then well mixed with stirring to obtain a 20% flowableconcentrate of each compound.

FORMULATION EXAMPLE 6 (Oil spray)

0.1 part of the compound (5) is dissolved in a mixture of 5 parts ofxylene and 5 parts of trichloroethane, and the resulting solution ismixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil spray.

Test examples will be shown below. In the examples, the presentcompounds used for test are shown by Compound Nos. in Table 2, andcompounds used as controls a control are shown by Compound symbols inTable 7.

                                      TABLE 7                                     __________________________________________________________________________    Compound                                                                      symbol                                                                              Structural formula            Remarks                                   __________________________________________________________________________    (A)                                                                                  ##STR678##                   Compound No. 800 described in EP No.                                          234,045-A2 234045A2.                      (B)                                                                                  ##STR679##                   Malathion                                 (C)                                                                                  ##STR680##                   Tridemorph                                __________________________________________________________________________

TEST EXAMPLE 1 Insecticidal test on pesticide-resistant green riceleafhopper (Nephotettix cincticeps)

Each test compound was formulated into an emulsifiable concentrateaccording to Formulation example 1, and rice stems (length, about 12 cm)were dipped for 1 minute in the 200-fold aqueous dilute solution (500ppm) of the emulsifiable concentrate. After air-drying, the rice stemswere put in a test tube, and 10 adults of resistant green riceleafhoppers were released in the test tube. After one day, the number ofdead and alive adults were established to obtain a morality. This testwas repeated twice.

The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Test compound  Mortality (%)                                                  ______________________________________                                         (2)           100                                                            (26)           100                                                            (34)           100                                                            (41)           100                                                            (42)           100                                                            (43)           100                                                            (50)           100                                                            (54)           100                                                            (119)          100                                                            (A)             0                                                             (B)             50                                                            No treatment    0                                                             ______________________________________                                    

TEST EXAMPLE 2 Insecticidal test on German cockroach (Blattellagermanica)

On the bottom of a polyethylene cup of 5.5 cm in diameter was placed afilter paper of the same size, and 0.7 ml of the 200-fold aqueous dilutesolution (500 ppm) of the emulsifiable concentrate, prepared from eachtest compound according to Formulation example 1, was dropped down tothe filter paper. About 30 mg of sucrose was put in the cup as a bait,and two male adult of German cockroach were released in the cup. Sixdays after covering the cup, the number of dead and alive adults wereestablished to obtain a mortality.

The results are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Test compound  Mortality (%)                                                  ______________________________________                                         (1)           100                                                             (2)           100                                                             (3)           100                                                             (5)           100                                                             (6)           100                                                            (17)           100                                                            (34)           100                                                            (35)           100                                                            (36)           100                                                            (41)           100                                                            (54)           100                                                            (56)           100                                                            (A)             0                                                             No treatment    0                                                             ______________________________________                                    

TEST EXAMPLE 3 Insecticidal test on tobacco cutworm (Spodoptera litura)

Each test compound was formulated into an emulsifiable concentrateaccording to Formulation example 1, and 2 ml of the 200-fold aqueousdilute solution (500 ppm) of the emulsifiable concentrate wasimpregnated into 13 g of artificial feeds for tabacco cutworm previouslyprepared in a polyethylene cup of 11 cm in diameter. Ten fourth instarlarvae of tabacco cutworm were released in the cup. After six days, thenumber of dead and alive larvae were established to obtain a mortality.This test was repeated twice. At the same time, the degree of attackupon the artificial feeds was also examined. The degree of attack wasjudged based on the following standard:

-: Little attack is observed.

+: Attack is observed.

++: Attack is heavy, few artificial feeds being left.

The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                        Test Compound                                                                              Mortality (%)                                                                             Degree of attack                                     ______________________________________                                         (1)         100         -                                                     (2)         100         -                                                     (3)         100         -                                                     (4)         100         -                                                     (5)         100         -                                                     (6)         100         -                                                     (7)         100         -                                                     (8)         100         -                                                    (14)         100         -                                                    (15)         100         -                                                    (16)         100         -                                                    (17)         100         -                                                    (19)         100         -                                                    (20)         100         -                                                    (21)         100         -                                                    (23)         100         -                                                    (25)         100         -                                                    (26)         100         -                                                    (28)         100         -                                                    (29)         100         -                                                    (30)         100         -                                                    (31)         100         -                                                    (32)         100         -                                                    (34)         100         -                                                    (35)         100         -                                                    (36)         100         -                                                    (37)         100         -                                                    (38)         100         -                                                    (39)         100         -                                                    (40)         100         -                                                    (41)         100         -                                                    (42)         100         -                                                    (43)         100         -                                                    (45)         100         -                                                    (47)         100         -                                                    (49)         100         -                                                    (50)         100         -                                                    (52)         100         -                                                    (54)         100         -                                                    (56)         100         -                                                    (57)         100         -                                                    (119)        100         -                                                    (122)        100         -                                                    (A)           30         ++                                                   No treatment  0          ++                                                   ______________________________________                                    

TEST EXAMPLE 4 Insecticidal test on common mosquito (Culex pipenspallens)

The emulsifiable concentrate of each test compound prepared according toFormulation example 1 was diluted 200 times with water, and 0.7 ml ofthe dilute solution was added to 100 ml of ion-exchanged water (activeingredient concentration, 3.5 ppm). Twenty last instar larvae of commonmosquito were released in the water, and after one day, the mortalitywas examined.

The standard for judging the effect was as follows:

Mortality (%)

a: Not less than 90%

b: Not less than 10% to less than 90%

c: Less than 10%

The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                        Test compound  Mortality (%)                                                  ______________________________________                                         (1)           a                                                               (2)           a                                                               (4)           a                                                               (5)           a                                                               (6)           a                                                               (7)           a                                                               (8)           a                                                              (14)           a                                                              (15)           a                                                              (16)           a                                                              (17)           a                                                              (19)           a                                                              (20)           a                                                              (21)           a                                                              (23)           a                                                              (24)           a                                                              (25)           a                                                              (26)           a                                                              (28)           a                                                              (29)           a                                                              (30)           a                                                              (31)           a                                                              (32)           a                                                              (34)           a                                                              (35)           a                                                              (36)           a                                                              (37)           a                                                              (38)           a                                                              (39)           a                                                              (40)           a                                                              (41)           a                                                              (42)           a                                                              (43)           a                                                              (44)           a                                                              (45)           a                                                              (46)           a                                                              (47)           a                                                              (48)           a                                                              (49)           a                                                              (50)           a                                                              (52)           a                                                              (54)           a                                                              (56)           a                                                              (57)           a                                                              (119)          a                                                              (120)          a                                                              (121)          a                                                              (122)          a                                                              (A)            c                                                              No treatment   c                                                              ______________________________________                                    

TEST EXAMPLE 5 Acaricidal test on carmine spider mite (Tetranychuscinnabarius)

Female adult carmine spider mites mite were parasitized, at a rate of 10adults/leaf, on potted kidney bean (in the primary leaf stage) 7 daysafter seeding, and placed in a constant-temperature room kept at 25° C.After 6 days, the emulsifiable concentrate of each test compoundprepared according to Formulation example 1 was diluted with water to anactive ingredient concentration of 500 ppm, and the dilute solution wassprayed onto the plant at a rate of 15 ml/pot on a turn table. At thesame time, the soil was drenched with 2 ml of the same dilute solution.After 8 days, the degree of damage to each plant by the mite wasexamined. The standard for judging the effect was as follows:

-: Little damage is observed.

+: Slight damage is observed.

++: Same damage as in the untreated plot is observed.

The results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                        Test compound  Effect                                                         ______________________________________                                         (1)           -                                                               (2)           -                                                               (3)           -                                                               (4)           -                                                               (5)           -                                                               (6)           -                                                               (7)           -                                                               (8)           -                                                               (9)           -                                                              (10)           +                                                              (11)           -                                                              (12)           +                                                              (13)           -                                                              (14)           -                                                              (15)           -                                                              (16)           -                                                              (17)           -                                                              (18)           -                                                              (19)           +                                                              (20)           -                                                              (21)           -                                                              (22)           +                                                              (23)           -                                                              (24)           -                                                              (25)           +                                                              (26)           -                                                              (27)           -                                                              (28)           -                                                              (29)           -                                                              (30)           -                                                              (31)           -                                                              (32)           -                                                              (33)           -                                                              (34)           -                                                              (35)           -                                                              (36)           -                                                              (37)           -                                                              (38)           -                                                              (39)           -                                                              (40)           -                                                              (41)           -                                                              (42)           -                                                              (43)           -                                                              (44)           -                                                              (45)           -                                                              (46)           +                                                              (47)           +                                                              (48)           +                                                              (49)           -                                                              (50)           -                                                              (51)           +                                                              (52)           -                                                              (53)           +                                                              (54)           +                                                              (55)           +                                                              (56)           -                                                              (57)           -                                                              (119)          +                                                              (120)          +                                                              (121)          +                                                              (122)          +                                                              No treatment   ++                                                             ______________________________________                                    

TEST EXAMPLE 6 Controlling test on blast of rice (Pyricularia oryzae)(preventive effect)

Plastic pots were filled with sandy loam, and rice (var., Kinki No. 33)was sowed and cultivated for 20 days in a greenhouse to obtain riceseedlings. The emulsifiable concentrates of the test compounds obtainedaccording to Formulation example 1 were each diluted with water to aprescribed concentration and foliar-applied onto the seedlings so thatthe spray liquor thoroughly adhered to the leaf surface. After thespraying, the seedlings were air-dried and inoculated by spraying aspore suspension of Pyricularia oryzae. After the inoculation, theseedlings were kept at 28° C. for 4 days at 28° C. under dark and veryhumid conditions, and then the controlling activity was examined.

The controlling activity was evaluated in the six stages describedbelow, 5, 4, 3, 2, 1 and 0, by macroscopically observing the conditionof the disease of the test plants, i.e. the degrees of colony andinfected area on the leaves, stems, etc., at the time of examination.

5: Colony or infected area is not observed at all.

4: About 10% of colony or infected area is observed.

3: About 30% of colony or infected area is observed.

2: About 50% of colony or infected area is observed.

1: About 70% of colony or infected area is observed.

0: More than about 70% of colony or infected area is observed, therebeing no difference in the condition of disease between the treated anduntreated plots.

The results are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                         (1)          200         5                                                    (2)          200         5                                                   (15)          200         4                                                   (16)          200         3                                                   (17)          200         5                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 7 Controlling test on sheath blight of rice (Rhizoctoniasolani) (preventive effect)

Plastic pots were filled with sandy loam, and rice (var., Kinki No. 33)was sowed and cultivated for 28 days in a greenhouse to obtain riceseedlings. The emulsifiable concentrates of the test compounds obtainedaccording to Formulation example 1 were each diluted with water to aprescribed concentration and foliar-applied onto the seedlings so thatthe spray liquor thoroughly adhered to the leaf surface. After thespraying, the seedlings were air-dried and inoculated by spraying adisc-inocular suspension of Rhizoctonia solani. After the inoculation,the sedlings were kept for 4 days under dark and very humid conditionsand then the controlling activity was examined based on the sameevaluation standard as in Test example 6.

The results are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                         (1)          200         4                                                   (24)          200         3                                                   (25)          200         4                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 8 Controlling test on powdery mildew of wheat (Erysiphegraminis f. sp. tritici)(curative effect)

Plastic pots were filled with sandy loam, and wheat (var., Norin No. 73)was sowed and cultivated for 10 days in a greenhouse to obtain wheatseedlings in the second 2nd leaf stage. The seedlings were inoculated bysprinkling with spores of Erysiphe graminis f. sp. tritici. After theinoculation, the seedlings were cultivated for 3 days in a greenhouse at23° C. Thereafter, emulsifiable concentrates of the test compoundsobtained according to Formulation example 1 were each diluted with waterto a prescribed concentration and foliar-applied onto the seedlings sothat the spray liquor thoroughly adhered to the leaf surface. After thespraying, the seedlings were cultivated for 6 days in a greenhouse at23° C., and the controlling activity was examined based on the sameevaluation standard as in Test example 6.

The results are shown in Table 15.

                  TABLE 15                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                        (1)           50          5                                                                 12.5        5                                                   (2)           50          5                                                                 12.5        5                                                   (C)           50          3                                                                 12.5        0                                                   ______________________________________                                    

TEST EXAMPLE 9 Controlling test on leaf rust of wheat. (Pucciniarecondita) (curative effect)

Plastic pots were filled with sandy loam, and wheat (var., Norin No. 73)was sowed and cultivated for 10 days in a greenhouse to obtain wheatseedlings in the second leaf stage. The seedlings were inoculated withspores of Puccinia recondita.

After the inoculation, the seedlings were cultivated for 1 day at 23° C.under very humid conditions. Thereafter, the emulsifiable concentratesof the test compounds obtained according to Formulation example 1 wereeach diluted with water to a prescribed concentration and foliar-appliedonto the seedlings so that the spray liquor thoroughly adhered to theleaf surface. After the spraying, the seedlings were cultivated for 6days at 23° C. in light, and the controlling activity was examined basedon the same evaluation standard as in Test example 6.

The results are shown in Table 16.

                  TABLE 16                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                         (1)          200         5                                                                 50          5                                                                 12.5        5                                                    (2)          200         5                                                                 50          5                                                                 12.5        5                                                    (5)          200         5                                                   (15)          200         5                                                   (16)          200         5                                                   (17)          200         5                                                   (21)          200         3                                                   (25)          200         3                                                   (26)          200         5                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 10 Controlling test on speckled leaf blotch of wheat(Septoria tritici) (curative effect)

Plastic pots were filled with sandy loam, and wheat (var., Norin No. 73)was sowed and cultivated for 8 days in a greenhouse to obtain wheatseedlings. The seedlings were inoculated by spraying with a sporesuspension of Septoria tritici. After the inoculation, the seedlingswere kept at 15° C. for 3 days under dark and very humid conditions andthen cultivated for 4 days under lighting. Thereafter, the flowableconcentrates of the test compounds obtained according to Formulationexample 5 were each diluted with water to a prescribed concentration andfoliar-applied onto the seedlings so that the spray liquor thoroughlyadhered to the leaf surface. After the spraying, the seedlings werecultivated for 11 days at 15° C. under lighting, and the controllingactivity was examined based on the same evaluation standard as in Testexample 6.

The results are shown in Table 17.

                  TABLE 17                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                         (1)          200         4                                                    (2)          200         4                                                   (17)          200         3                                                   (21)          200         3                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 11 Controlling test on late blight of tomato (Phytophthorainfestans) (preventive effect)

Plastic pots were filled with sandy loam, and tomato (var., Ponteroza)was sowed and cultivated for 20 days in a greenhouse to obtain tomatoseedlings. The wettable powders of the test compounds obtained accordingto Formulation example 2 were each diluted with water to a prescribedconcentration and foliar-applied onto the seedlings so that the sprayliquor thoroughly adhered to the leaf surface. After the spraying, theseedlings were inoculated by spraying the spore suspension ofPhytophthora infestans. After the inoculation, the seedlings were keptat 20° C. for 1 day under very humid conditions and then cultivated for5 days in light. The controlling activity was then examined based on thesame evalutation standard as in Test example 6.

The results are shown in Table 18.

                  TABLE 18                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                         (1)          200         4                                                                 50          4                                                                 12.5        3                                                    (2)          200         5                                                   (16)          200         4                                                   (17)          200         4                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 12 Controlling test on alternaria spot of Japanes radish(Alternaria brassicicola) (preventive effect)

Plastic pots were filled with sandy loam, and Japanese radish (var.,Wase-40 nichi) was sowed and cultivated for 5 days in a greenhouse toobtain Japanese radish seedlings. The wettable powders of the testcompounds obtained according to Formulation example 2 were each dilutedwith water to a prescribed concentration and foliar-applied onto theseedlings so that the spray liquor thoroughly adhered to the leafsurface. After the spraying, the seedlings were inoculated by sprayingwith a spore suspension of Alternaria brassicicola. After theinoculation, the seedlings were kept at 23° C. for 1 day under veryhumid conditions and then cultivated for 3 days in a greenhouse. Thecontrolling activity was then examined based on the same evaluationstandard as in Test example 6.

The results are shown in Table 19.

                  TABLE 19                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                        (1)           200         5                                                                 50          4                                                                 12.5        3                                                   (2)           200         5                                                                 50          5                                                                 12.5        4                                                   (C)           200         0                                                   ______________________________________                                    

TEST EXAMPLE 13 Controlling test on downy mildew of cucumber(Pseudoperonospora cubensis) (curative effect)

Plastic pots were filled with sandy loam, and cucumber (var.,Sagamihanjiro) was sowed and cultivated for 14 days in a greenhouse toobtain cucumber seedlings in the cotyledonous stage.

The seedlings were inoculated by spraying with a spore suspension ofPseudoperonospora cubensis. After the inoculation, the seedlings werekept at 20° C. for 1 day under very humid conditions. Thereafter, thewettable powders of the test compounds obtained according to Formulationexample 1 were each diluted with water to a prescribed concentration andfoliar-applied onto the seedlings so that the spray liquor thoroughlyadhered to the leaf surface. After the spraying, the seedlings werecultivated for 8 days in light, and then the controlling activity wasexamined based on the same evaluation standard as in Test example 6.

Test results are shown in Table 20.

                  TABLE 20                                                        ______________________________________                                        Test          Concentration                                                                             Controlling                                         Compound      (ppm)       activity                                            ______________________________________                                        (1)           200         5                                                   (2)           200         5                                                   (5)           200         3                                                   (21)          200         3                                                   (26)          200         5                                                   (C)           200         0                                                   ______________________________________                                    

What is claimed is:
 1. A compound represented by the formula, ##STR681##wherein each of R₄ and R₅, which may be the same or different, is ahydrogen atom or an alkyl group; and R'₆ is a hydrogen atom, or analkyl, haloalkyl, alkenyl, alkoxyalkyl or alkylthioalkyl group, or anoptionally substituted cycloalkyl, cycloalkenyl, phenyl or pyridylgroup.